Home

WSolids1 User Manual - Pascal-Man

1. 80 212 20 Spina Pregtiene oec u se nahen nenn 80 312 21 Speedy Calculator Bene ee dd aan 80 4 Acknowledgements 81 dl Credib 222 0 288 eee a tpr ADR G ppi ke BADE p nen 81 42 Trademark Acknowledgements o an ran ee 82 43 Copy AMON u e Rs Oe Re Re ee SHG ea S 82 44 Disclaimer ot Warranty oos ecs ua a aa aoa a ae en A E E R E 82 4 January 6 2009 1 Getting Started Contents 1 1 1 2 1 3 1 4 1 5 Introduction cocina 6 111 Purpose atthe Program 2 02 2 Iada Tadei a i eR EES 6 LUZ POMUT S soosoo sawi a a aE ORE ee He Dawe a eee bed 7 DS Teer ee oe ee a Weert a eee Dea aS GR aS GR a 7 1142 Trouble 3 crot Ge gb Gee ana ee ee ea Bee 8 ICALI a op st AREA AA ATLAS 9 REO ASIS u ade a A ea Se a E 10 1 31 Version 1 19 2 21082008 o ooe saae esse naar ee a 10 132 Versi n 1 17 30 23 052001 sic 22 32 22 taid eee ern he de 10 Loa Version 1 17 28 27092000 a Ka Se eek ee nn ae ae GS Dad 10 1 34 Version 1 17 22 17 091999 24 60 3 Casa ta a ra Ee W a wae a ee eS 10 135 Version 1 17 21 09 10 1998 2 coca Dena rea GR aop eS 10 13 Verion lIr ook Geos eee tee be aea bi abe e a a ebb ha 11 foe Voron ll an te oe pad de hed dk Wa eee See Yew se ele 11 Multiple Document Interface MDI 1 1 ee eee 12 141 The Multiple Document Interface u 6 02 52 028 ce ee Ree Se a 12 342 e A 12 123 Keks DB a aia ta ae 13 Keyboard Accelerators oo ooo ooo o ooo ooo om o
2. MAS Spin 1 2 Coupled to Quadrupolar Nucleus Diag Site 2 y Tie to previous site Coupled to _ Speedy calculation N A Spin 3 2 Delta iso ppm D Hz alpha o deg Hz Beta D deg Delta J Hz Ru Yo Help y U Y in d Y ip Q J a T T Figure 3 7 Experimental and calculated 1 C MAS NMR spectra of a carbon coupled to 9 7Cl LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Background The quadrupolar interaction at a quadrupolar nucleus causes its axis of quantization to be tilted away from the direction of the external magnetic field This also modifies the spatial dependence of the dipolar interaction so that magic angle spinning is not able to suppress the heteronuclear dipolar coupling in the spectrum of the spin 1 2 nucleus resulting in splittings and broadenings Similar effects can be transmitted through the indirect spin spin coupling If the nuclear quadrupolar coupling constant is on the same order of magnitude as the Larmor frequency of the quadrupolar nucleus the combined Zeeman quadrupolar Hamiltonian must be diagonalized at each orientation and averaged over a rotor period to calculate a theoretical spectrum 3 7 1 Implementation Details Specifically we use the following conventions e the NQR not
3. 14 Chapter 1 Getting Started 1 1 Introduction 1 1 1 Purpose of the Program WSolids1 is a program for the visualization and analysis of processed one dimensional solid state NMR data It is a simulation package initially developed at the Department of Chemistry p 6 Dal housie University p 7 Halifax Canada in order to deal with the multitude of interactions observed in NMR spectra of static or spinning solid samples The initial versions have been written in C using Borland C 4 5 However in spring 2008 the developments or the lack of such at Borland made me change my programming tools to Microsoft Visual C 2008 Express Edition Not that this development environment has everything that I would need to work efficiently but it is for free it s like they give you a free car without a seat for the driver it s workable but a bit bumpy at times WSolids1 succeeds its earlier FORTRAN version Solids Although there are several general purpose programs or libraries available to calculate many in teractions and for many different experiments there is still room for programs with specially de signed specific calculation models The main reason is efficiency A routine designed for one par ticular purpose will always be more efficient than a general purpose routine Progress in comput ing power continually decreases the gap However calculation of a static powder pattern of an iso lated spin pair using a
4. Chapter 1 Getting Started 1 2 Overview The Overviews provided here are aimed at giving an outline of the steps required to achieve a par ticular task Following a question in the left column links to the relevant topics are provided After catching up on any specific topic use the Back feature of your reader to return to this screen How do I start Create a new spectrum window p 18 Read an experimental spectrum p 18 Create a new spin system p 31 Define convolution parameters p 28 Calculate p 33 Repeat as required p 33 Save the results p 22 GOEGeCH8O How do I work efficiently Use keyboard accelerators p 14 Use the cycle feature p 33 9 January 6 2009 Chapter 1 Getting Started 1 3 Revision History This page describes changes made to the WSolids1 program versus previous versions and provides a summary of new features 1 3 1 Version 1 19 2 21 08 2008 e This is the first 32 bit release Internally Wsolids1 underwent some serious changes that will not be apparent to the user e Added reading of TopSpin XWinNMR p 19 JCAMP DX p 21 and Simpson p 22 files removed handling of Antiope NMRLAB and CC2X files e In addition to WinNMR format spectra can also be saved as TopSpin or Solids files Incorporated the IUPAC Recommendations 2001 for the NMR properties of NMR active isotopes the new Q values from Pyykk fixed spin of Nd 145 and U 235 and added U 233 e MAS S
5. nmrguest 4ok01ehm 20 1 N N lt dir gt data lt user gt nmr lt name gt lt expno gt pdata lt procno gt el pdata proc acqu procs acqus 1r 1i or Zrr fid or ser outd pulseprogram title Those parts of the path name written in red letters are fixed names that are required by TopSpin XWinNMR A data set of name lt name gt consists of one or more spectra each characterized by its experiment num ber lt expno gt an integer Each spectrum can have different processed data stored in the pdata subdi rectory under a specific processing number lt procno gt an integer that is usually 1 In order to be recognized by WSolids as TopSpin XWinNMR file the data files need to adhere to the following format e 1r in binary floating point format needs to be present 19 January 6 2009 Chapter 2 Menus e procs needs to be present in the same directory and acqus two levels higher both are ASCII parameter files of variable record length and start with JCAMP DX format the acqus file contains the parameters SFO1 SW_h O1 AQ_mod BYTORDA TD DECIM DSPFVS NC NUCLEUS and procs contains OFFSET SI XDIM BYTORDP NC_proc Bruker WINNMR Generic This was the file format used by BRUKER s WIN NMR version 4 0 1D version and is still produced by Bruker s GetFile utility if conversion of Aspect files is selected basically the parameter files are in binary format In order to be recognized by WSol
6. 2009 Chapter 3 Spin Systems the assignment of values to the principal axes will affect the spectrum 3 12 5 Herzfeld Berger Convention dis Isotropic Value digg 811 622 933 3 Span Q n 633 N20 Skew x 3 922 digo O 1 lt x lt 1 In the Herzfeld Berger notation 4 a tensor is described by three parameters which are combinations of the principal components in the standard notation The isotropic value i e the center of gravity is the average value of the principal components The span describes the maximum width of the powder pattern The skew of the tensor is a measure of the amount and orientation of the asymmetry of the tensor As indicated x is given by 3a 2 Depending on the position of 522 with respect to digo the sign is either positive or negative If 0 2 equals iso a and the skew are zero In the case of an axially symmetric tensor d22 equals either 911 or 633 and a Q 3 Hence the skew is 1 The parameter u used with the Herzfeld Berger tables is related to the span of a tensor by u O SF spinning rate The parameter p used with the Herzfeld Berger tables corresponds to the skew of a tensor described here For historical reasons we used p throughout this manual but generally we prefer x 3 The Herzfeld Berger convention is related to the Standard convention via 022 digo K O 3 933 3 diso 622 O 2 911 3 iso 22 633 3 12 6 Haeberlen
7. 4 2 692 diso 1 4 2 633 digo 6 1 4 2 11 biso 1 y 2 References 1 Pure Appl Chem 1972 29 627 1976 45 217 2 Some examples for established shielding scales Carbon A K Jameson C J Jameson Chem Phys Lett 1987 134 461 W T Raynes R McVay S J Wright J Chem Soc Faraday Trans 2 1989 85 759 Silicon C J Jameson A K Jameson Chem Phys Lett 1988 149 300 Phosphorus C J Jameson A De Dios A K Jameson Chem Phys Lett 1990 167 575 Tin A Laaksonen R E Wasylishen J Am Chem Soc 1995 117 392 3 J Mason Solid State Nucl Magn Reson 1993 2 285 4 J Herzfeld A E Berger J Chem Phys 1980 73 6021 5 U Haeberlen In Advances in Magnetic Resonance Suppl 1 J S Waugh Ed Academic Press New York 1976 M Mehring Principles of High Resolution NMR in Solids 2nd ed Springer Verlag Berlin 1983 3 12 7 Chemical Shift and Chemical Shielding It is recommended that the IUPAC conventions 1 are obeyed e The absolute chemical shielding 7 in ppm is the difference in shielding between the frequency of the bare nucleus v uc and the frequency of the same nucleus in the species under investiga tion Vs o ppm 1e06 Unucl Vs Vnual e The chemical shift is the difference in shielding between the nucleus in the species under investigation os and the shielding of the same nucleus in a reference c
8. 50 4914 52 January 6 2009 Chapter 3 Spin Systems 3 5 MAS Chemical Shift Anisotropy HB Chemical Shift Anisotropy Site 5 Rel Intensity LAUU _ Tie to previous site Convention STANDARD v MAS freq 1000 000 Delta 11 100 000 Delta 22 50 000 Delta 33 100 000 This model calculates the spectrum of a powder sample spinning at the magic angle showing only chemical shift anisotropy Spinning sideband intensities are obtained from precomputed Herzfeld Berger Tables Parameter Purpose Rel Intensity p 70 Relative intensity of this site in percent Tie to previous site p 70 Ties parameters to those of the previous site MAS freq p 80 Spinning frequency in Hz Convention p 70 Convention used for chemical shift tensor compo nents Delta 11 Delta 22 Delta Principal components of chemical shift tensor stan 33 p 70 dard convention in ppm Delta iso Span Skew p Principal components of chemical shift tensor 70 Herzfeld Berger convention Delta iso Anisotropy Principal components of chemical shift tensor Hae Asymmetry p 70 berlen convention LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Background In addition to the chemical shift anisotropy CSA the spectrum of a spin in a powder sample under
9. HB Quadrupolar nucleus Spin 1 2 Spin S Diag Spin 1 2 Spin S Stick ZJ x te The Select Calculation Model dialog box available from the New Site p 31 item of the Simulation p 24 popup menu allows the user to select a calculational model from a list of available models Each model is in its performance tailored to a specific situation Currently the following models are supported Model Characteristics Static Chemical shift Spectrum of a static powder sample showing chem anisotropy p 43 ical shift anisotropy powder pattern Static Dipolar chemical Chemical shift anisotropy direct dipole dipole cou shift A2 AX p 45 pling and indirect spin spin coupling for a homonu clear pair of equivalent spin 1 2 nuclei or a het eronuclear spin pair in a static powder sample A2 or AX approximation Static Dipolar Chemical Chemical shift anisotropy direct dipole dipole cou Shift AB p 48 pling and indirect spin spin coupling for a homonu clear pair of spin 1 2 nuclei including second order effects in a static powder sample AB 31 January 6 2009 Chapter 2 Menus Static Quadrupolar Nu cleus p 50 MAS Chemical shift anisotropy HB p 53 MAS Quadrupolar nu cleus p 56 MAS Spin 1 2 Spin S Diag p 58 MAS Spin 1 2 Spin S Stick p 61 MAS Spin 1 2 Spin S Shape p 64 VAS Dipolar chemical shift A2 AX p 66 V
10. Kirby R E Wasylishen Nuclear Magnetic Shielding Tensors for the Carbon Nitrogen and Selenium Nuclei of Selenocyanates A Combined Experimental and Theoretical Approach Can J Chem 2000 78 614 625 65 January 6 2009 Chapter 3 Spin Systems 3 10 VAS Dipolar Chemical Shift A2 AX VAS Dipolar Chemical Shift Spin Pair Site 2 Coupled to Ir 193 zi Rel Intensity LUAU Spin 3 2 N 34 000 _ Tie to previous site Convention STANDARD Homonuclear D 1500 000 YAS angle 60 000 deg J 60 000 Delta 11 100 000 ppm Delta J 0 000 Hz Delta 22 50 000 ppm Alpha 0 000 deg Delta 33 100 000 ppm Beta 20 000 deg Spectrum of a powder sample under variable angle spinning containing a spin pair where AX or A2 approximation is valid Background In addition to the chemical shift anisotropy CSA the spectrum of a spin pair will also depend on the direct dipolar coupling and potentially the indirect spin spin coupling between both nuclei Because both the CSA and dipolar interaction are tensorial interactions the actual line shape also depends on their relative orientation Spinning the powder sample rapidly about an axis that forms an angle different from the magic angle with respect to the external magnetic field the resulting lineshape will look like that of a static powder sample but scaled by a factor that depends on the spinning angle This scaling factor ran
11. Orer References 1 Pure Appl Chem 1972 29 627 1976 45 217 2 Some examples for established shielding scales Carbon A K Jameson C J Jameson Chem Phys Lett 1987 134 461 W T Raynes R McVay S J Wright J Chem Soc Faraday Trans 2 1989 85 759 Silicon C J Jameson A K Jameson Chem Phys Lett 1988 149 300 Phosphorus C J Jameson A De Dios A K Jameson Chem Phys Lett 1990 167 575 Tin A Laaksonen R E Wasylishen J Am Chem Soc 1995 117 392 3 C J Jameson Solid State Nucl Magn Reson 1998 11 265 3 12 8 Coupled To In some models the observed nucleus is coupled to another nucleus via indirect spin spin or direct dipole dipole coupling The coupled nucleus can be selected from a list of available isotopes In some cases this also updates an entry with the natural abundance p 73 of the selected isotope as well as the spin of this nucleus 3 12 9 Natural Abundance By default this parameter is set to the natural abundance of an isotope in percent This parameter can however be changed to reflect isotopic enrichment 3 12 10 Dipolar Coupling Constant D The direct dipole dipole coupling is the through space interaction between the magnetic moments of nuclei The magnitude of this interaction is characterized by the Dipolar Coupling Constant given in Hz It depends on the inverse cube of the distance between the interacting nuclei besides some natural
12. p 25 box Background If the nuclear quadrupolar coupling for a quadrupolar nucleus is sufficiently large MAS cannot re move its effect on the line shape of the central transition and causes second order broadening with characteristic lineshapes as well as a second order shift In order to obtain correct chemical shifts for the quadrupolar nucleus simulation of the spectra is required Optionally indirect coupling to a heteronucleus can be added note quadrupolar interaction if any is neglected for the coupled het eronucleus 3 6 1 Implementation Details Specifically we use the following convention 56 January 6 2009 Chapter 3 Spin Systems EI Eile Simulation Tools Window Help 18 x MAS Quadrupolar Nucleus 2nd order x Site 1 Rel Intensity NIKI Fe LB _ Fie te previeus site Eta Delta iso 1825 200 ppm Coupled to Spin 172 N A 100 000 J Hz m Jl El Figure 3 6 Experimental and calculated Mo MAS NMR spectra of a powder sample of a molybdenum phosphine complex e the NOR notation is used for labelling the axes of the EFG tensor VZZ gt VYY gt VXX Figure 3 6 shows an example for the succesful simulation of a MAS spectrum of a quadrupolar nucleus that shows the combined effect of quadrupolar interaction and spin spin coupling to a spin 1 2 nu cleus in a powder sample It is the 95Mo NMR MAS spectrum of pentacarbonyl
13. y 2 The rotation matrix to describe this operation is given by cosp 0 sin R B 0 1 0 sing 0 cosp The last rotation involves the Euler angle y The x 3 y 3 z 3 axis system is rotated about the z 3 axis through an angle y counterclockwise to generate the final coordinate system x y z Analogously to the first Euler rotation this mixes the coordinates along x 3 and y 3 while the coordinate along z 3 remains unaffected The rotation matrix to describe this operation is given by cosy siny 0 Ry siny cosy 0 0 Y 4 77 January 6 2009 Chapter 3 Spin Systems The combined effect of these three rotations is given by this transformation matrix Rv RAB 2 0 cosacosBcosy sinwsiny sinocosfcosy cosesiny sin cosy cosaecosksiny sinecosy sinoecosBsiny cosecosy sinBsiny cosasin s sinasin cosp Note This type of rotation about sequentially newly generated axes produces the same result as rota tions by the same angles about the fixed original axes cf Mehring s book appendix 3 12 16 The Swivel Chair The following humorous explanation of how to transform from one coordinate system to the other by using Euler angles has been posted to the newsgroup comp graphics algorithms by John Aspinall jga harlequin co uk Subject Rotation matrix gt angles an aside on 16 Feb 1996 21 21 04 GMT some editing was made here to make the explanation conform to the convention used here Many people s
14. 2 2 8 Active Only The item Active only of the Simulation p 24 popup menu determines if a calculation is performed for the currently active window only or for all available spectrum windows 2 2 9 Cycle The item Cycle of the Simulation p 24 popup menu automatically initiates the next step in the generation of a calculated spectrum to refine the agreement between experimental and theoretical spectra The detailed course of the cycle feature depends on the selections made under Cycle options p 33 Note The Enter key is the accelerator key for this action 2 2 10 Cycle Options Cycle Options Cycle through MV Default parameters M Site parameters M Convolution parameters V Calculation Fe de to 33 January 6 2009 Chapter 2 Menus The item Cycle options of the Simulation p 24 popup menu allows to customize the detailed course of the Cycle p 33 feature This cycle consists of Selection Action Windows After all other cycle steps were performed for a win dow switch to the next spectrum window Default parameters Edit the spectrum default parameters for the cur rently active spectrum window Site parameters Edit the site specific parameters for each available site Convolution parameters Edit the convolution parameters Calculation Perform calculation of a theoretical spectrum and display the result 34 January 6 2009 Chapter 2 Menus 2 3 Tools Menu The Tools pop up
15. 5 methyldibenzophosphole molybdenum 0 Mo CO 5 MeDBP and the results have been published in K Eichele R E Wasylishen J H Nelson Solid State 95Mo NMR Studies of Some Prototypal Molybdenum Compounds Sodium Molybdate Dihydrate Hexacarbonylmolybdenum and Pentacarbonyl Phosphine Molybdenum 0 Complexes J Phys Chem A 1997 101 5463 5468 3 6 2 References 1 The second order expression is taken from Amoureux s treatment which follows Taulelle Amoureux Fernandez Granger In Multinuclear Magnetic Resonance in Liquids and Solids Chemi cal Applications Granger Harris eds Kluwer Academic Publishers 1990 Ch 22 p 409 57 January 6 2009 Chapter 3 Spin Systems 3 7 MAS Spin 1 2 Spin S Diag MAS Spin 1 2 Coupled to Quadrupolar Nucleus Diag Site 2 _ Tie to previous site Coupled to _ Speedy calculation N A 100 000 Spin 3 2 Delta iso 0 000 ppm E 510 000 Hz Alpha D 0 000 deg 20 000 Hz Beta D 0 000 deg 0 000 Hz Spectrum of a powder sample under magic angle spinning containing a spin 1 2 nucleus dipolar and indirect coupled to a quadrupolar nucleus The expectation values for the spin states of the quadrupo lar nucleus are evaluated using full matrix diagonalization Only the center peak in the spectrum is Chi 73 000 MHz Eta 0 000 calculated i e high spinning frequency limit cleus Note Don t forget to define the observe
16. 79 CTST p 80 Coupled to p 73 N A p 73 D p 73 J p 73 Delta J p 74 Alpha p 74 Relative intensity of this site in percent Ties parameters to those of the previous site Convention used for chemical shift tensor compo nents Principal components of chemical shift tensor stan dard convention in ppm Principal components of chemical shift tensor Herzfeld Berger convention Principal components of chemical shift tensor Hae berlen convention Euler angles in degrees for going from the electric field gradient tensor frame to the principal axis sys tem of the chemical shift tensor Quadrupolar coupling constant in MHz Asymmetry parameter of the electric field gradient tensor 0 lt eta lt 1 Select central transition CT or satellite transitions ST Specifies the nucleus the observed nucleus is cou pled to Only heteronuclear coupling will be con sidered Natural abundance in percent of the coupled nu cleus If smaller than 100 WSolids1 automatically includes calculation of the spectrum of the uncou pled spin species Direct dipole dipole coupling constant in Hz Indirect spin spin coupling constant in Hz Anisotropy of the indirect spin spin coupling in Hz Azimuth angle in degrees of the internuclear vec tor in the principal axis system of the electric field gradient tensor 50 January 6 2009 Chapter 3 Spin Systems iol x Eile Simulation Tool
17. ASCII text file usually with extension SPE WSolids1 requires the parameters SIMP NP SW and in newer versions REF Reference 1 M Bak J T Rasmussen N C Nielsen J Magn Reson 2000 147 296 Varian Reading of Varian files is planned but not implemented yet Basically I would need some example files 2 1 3 Save Spectrum The Save Spectrum item of the File p 18 pop up menu saves a spectrum from the active Spectrum Window p 18 If the spectrum window contains only an experimental spectrum the experimental spectrum is saved If there is a calculated spectrum available the calculated spectrum is always saved There are several output formats available 1 a WinNMR p 20 file with UNIX type ASCII parameter files 2 in TopSpin XWinNMR p 19 format 3 in Solids p 21 format ASCII and JCAMP are planned but not implemented yet When writing WinNMR files the file name should adhere to the eeeppp p 20 convention When writing Topspin files please consider that the dialog was written initially for WinNMR There fore if you want to crate the file d u data nmrguest nmr simulation 11 pdata 20 1r you should point the path to the simulation subdirectory and enter the file name 011020 file type Topspin WSolids1 extracts from this file name the corresponding experiment and processing numbers Note When displaying experimental spectra and spectra calcu lated by WSolids1 in WinNMR use the relat
18. Convention Principal Components 5zz disol gt rr diol gt Sy iso 180 5 Isotropic Value iso 11 522 033 3 Reduced Anisotropy 627 iso Anisotropy Ag z 0xx yy 2 Ag 36 2 Asymmetry y yy xx 0 lt 7 lt 1 The Haeberlen Mehring 5 convention uses different combinations of the principal components to describe the line shape This convention requires that the principal components are ordered according to their separation from the isotropic value The center of gravity of the line shape is described by the isotropic value which is the average value of the principal components The anisotropy and reduced anisotropy describe the largest separation from the center of gravity The term reduced anisotropy is not used in the literature but we introduce it here in order to be able to distinguish between and Ag The sign of the anisotropy indicates on which side of the isotropic value one can find the largest separation 71 January 6 2009 Chapter 3 Spin Systems The asymmetry parameter indicates by how much the line shape deviates from that of an axially symmetric tensor In the case of an axially symmetric tensor a dyy xx will be zero and hence 7 0 The Haeberlen Mehring convention is related to the Standard convention via for gt 0 i e 077 011 for lt 0 i e zz 033 911 diso 033 liso 6 622 digo 6 1
19. MAS NMR spectrum of NMe4 2 Cd SCN 4 where the octahedral cadmium is coupled to four N 14 nuclei and the results have been published in K Eichele R E Wasylishen High Resolution 113Cd CP MAS NMR Studies of Cadmium Thiocyanate Coordination Compounds Direct Observation of 113Cd 14N Spin Spin Coupling Constants in the Solid State Inorg Chem 1994 33 2766 2773 62 January 6 2009 Chapter 3 Spin Systems MAS Spin 117 000 6 200 117 000 6 200 67 000 4 000 67 000 4 000 Figure 3 8 Experimental and calculated 3Cd MAS NMR spectra showing coupling to 4N 63 January 6 2009 Chapter 3 Spin Systems 3 9 MAS Spin 1 2 Spin S Shape Spectrum of a powder sample under magic angle spinning containing a spin 1 2 nucleus spin spin coupled to a quadrupolar nucleus The expectation values for the spin states of the quadrupolar nu cleus are evaluated using first order perturbation theory where the quadrupolar interaction is the perturbation Only the center peak in the spectrum is calculated i e high spinning limit Note Don t forget to define the observed nucleus this is re quired to evaluate the Larmor frequency of the quadrupolar nu cleus Note For a nucleus with a nuclear spin of 3 a warning will ap pear that the spectrum contains a single line subspectrum Ac cording to the line shape equation this will generally be true of two transitions and independent of the paramet
20. This orientation dependence of the chemical shift is referred to as chemical shift anisotropy CSA Mathematically the chemical shift anisotropy is described by a second rank tensor a 3 by 3 matrix which in the case of the symmetric part of the chemical shift CS tensor consists of six independent components Generally one is able to express the chemical shift tensor in a coordinate frame where all off diagonal elements vanish In this principal axis system the chemical shift tensor is fully described by the three diagonal elements the principal components and the three eigenvectors or Euler angles describing Chapter 3 Spin Systems E Ele Simulation Tools Window Help Chemical Shift Anisotropy x Site 1 Rel Intensity LA _ Tie te previeus site Convention Herzfeld Berger E Delta iso Skew Figure 3 1 Experimental and calculated 3 P NMR spectra of a static powder sample of a molybdenum phosphine complex the orientation of the principal axes with respect to an arbitrary frame Due to the chemical shift anisotropy the spectrum of a static powder sample where statistically all orientations of the molecule with respect to the magnetic field are present will consist of a broad line shape with three distinct features corresponding to the principal components However note that for a powder sample there is no information about the orientation of the principal components in th
21. all sites Spectrum Default Parameters SF 100 0000 MHz Hz ppm Nucleus P 31 je 20000 0000 Hz Sk 1024 Pts 2 20000 0000 Hz V Use relative threshold value Derivative Mode l Site dependent broadening No C Ist C 2nd EES The default parameters define Parameter Purpose Nucleus p 25 Observed nucleus SF p 25 Spectrometer frequency Larmor frequency in MHz SI p 26 Size of calculated spectrum in points ppm Hz p 26 Toggles input for F1 F2 between Hz or ppm F1 p 26 High frequency limit of calculated spectrum F2 p 26 Low frequency limit of calculated spectrum Use relative threshold Toggle between use of a threshold value in the con value p 27 volution or doing the full convolution Site dependent broaden Individual or global line broadening ing p 27 Derivative Mode p 30 Absorption or derivative display Observed Nucleus The kind of observed nucleus is selected in the Spectrum Default Parameter p 25 box In many cases the actual selection here is not important Exceptions are for example e Observation of a quadrupolar nucleus here the nuclear spin quantum number is important e If a quadrupolar nucleus is coupled to the observed nucleus the ratio of magnetogyric ratios of both nuclei is used to calculate the Larmor frequency of the quadrupolar nucleus Spectrometer Frequency The parameter SF defines the spectrometer or Larmor frequency in MHz and
22. anisotropy 41 42 44 46 48 chi 66 convention 57 59 convolution 26 28 35 copyright 70 coupling 60 61 credits 69 cycle 32 D 34 60 derivative 29 dipolar 42 44 dipolar coupling 60 dipolar coupling constant 34 disclaimer 70 edit site 32 electric field gradient 66 elements 35 eta 66 Euler angles 62 65 66 F1 26 F2 26 features 6 files 18 22 gamma 34 Gaussian 28 Haeberlen 57 help 38 Herzfeld Berger 48 57 heteronuclear 42 46 49 50 52 54 55 history 10 homonuclear 42 44 46 55 56 Hz 25 indirect coupling 60 61 intensity 57 introduction 6 9 isotopic labelling 60 J 60 61 JCAMP DX 21 keyboard 14 Larmor frequency 25 license 6 line broadening 27 28 Lorentzian 28 MAS 48 50 52 54 67 MDI 12 menus 15 model 31 multiple documents 12 multiple spectra 12 natural abundance 34 60 nuclear properties 34 nuclei 35 nucleus 25 offset 36 overview 9 periodic system 35 polar angles 61 ppm 25 problems 39 program version 38 Q 34 quadrupolar 46 49 50 52 54 R 34 Index reverse spectrum 36 revision 10 rotations 62 65 66 satellite transition 67 scaling 35 SF 25 shielding 59 shift 59 SI 25 Simpson 22 simulation 24 site 30 32 SOLIDS 21 spectrometer frequency 25 spectrum 18 22 24 26 35 36 spectrum size 25 spin 34 spin pair 42 44 46 49 50 52 54 56
23. dipole dipole coupling Therefore one cannot determine both interactions separately in an experiment only an effective dipolar coupling constant Depp u a However one could calculate the dipolar coupling constant p 73 from known internuclear sepa rations cf Calculate Dipolar Coupling Constant p 34 For an AX spin system the prefactor x of the equation above equals one x 1 while for a pair of magnetically equivalent spins this factor corresponds to 3 2 x 1 5 Note For an A2 spin system the isotropic part of the indirect spin spin cou pling p 73 does not contribute to the spectrum but the anisotropy of the indirect spin spin coupling does 3 12 13 Polar Angles Polar angles are used to define the orientation of a vector in a three dimensional Cartesian coordinate system x y z as shown in this figure describing the orientation of the internuclear vector r in the principal axis system of the chemical shift tensor The azimuthal angle alpha is the angle between the x axis d11 and the projection of the vector into the x y plane d11 d22 equatorial plane The polar angle beta is the angle between the vector and the z axis d33 pole The polar angles are closely related to the type of Euler angles p 75 used by WSolids1 Because the dipolar interaction is 74 January 6 2009 Chapter 3 Spin Systems axially symmetric the two polar angles are sufficient to describe the
24. general purpose program still requires several hours as compared to the few seconds using the less general implementation in WSolids the several hours was written in the mid end nineties in 2008 this difference has dwindled The advantage for the user is convenience rather than power not every user has the knowledge to feel comfortable with for example Simpson http www bionmr chem au dk bionmr software simpson php i Figure 1 1 The Department of Chemistry at Dalhousie University Halifax Canada 6 January 6 2009 Chapter 1 Getting Started Figure 1 2 The logo of Dalhousie University Halifax Canada 1 1 2 Features This section lists some of the features of WSolids1 the knowledge of which should enable the user to work more efficiently with WSolids1 e WSolids1 uses the Multiple Document Interface p 12 MDI specification The user should familiarize himself with this specification Often the vendors of NMR spectrometers provide some means of analyzing or simulating experimental spectra but often a mere simulation to answer a question like how would this look like without an experimental spectrum is not possible MDI as implemented in WSolids1 allows to calculate spectra for different external magnetic fields different derivative modes or different experimental conditions simultaneously using the same spin system parameters This could help to answer a question like does it
25. horizontal w r t the room Rotation 3 About the Z axis Turn your head Try not to fall out of your chair Final coordinate system Z coming out of the top of your head points at any desired point The final rotation has allowed you to point your nose X in any direction perpendicular to Z You can think of the three angles as azimuth altitude tilt or longitude latitude tilt or whatever An additional advantage of the Z Y Z formulation is that its inverse is also in the same Z Y Z formula tion 78 January 6 2009 Chapter 3 Spin Systems 3 12 17 Determining Euler Angles Given the relative orientations of two coordinate systems how does one go about determining the Euler angles relating them First one needs to decide which coordinate system to take as the reference coordinate system X Y Z and which one as derived coordinate system x y z Because the Euler transformations allow to switch between coordinate systems easily it does not matter which one is selected The angle is simply the angle between the z axes of both coordinate systems The angle a is the angle between the X axis of the reference coordinate system and the projection of z into the X Y plane Finally y is the angle between the y axis and the line of nodes 3 12 18 Electric Field Gradient Tensor A quadrupolar nucleus S with nuclear spin S gt 1 2 is subject to an interaction of the nuclear quadrupole moment eQ with the
26. in one shaded area all parameters outside this area depend on the state of the check box exceptions are e g spin quantum numbers 3 12 3 Convention Unfortunately there are many different conventions around in the literature for labeling the principal components of chemical shift tensors Most of the conventions have advantages for certain situations but drawbacks in others Often it is not obvious which convention has been chosen The collection given here attempts to summarize some of the most frequently used conventions 3 12 4 Standard Convention Principal Components 011 gt 077 gt 633 011 lt 022 lt 033 Isotropic Value iso 641 622 933 3 Ciso 011 072 033 3 In what we shall call the standard convention the principal components of the chemical shift tensor 641 022 and 633 are labeled according to the IUPAC rules 3 They follow the high frequency positive order Thus 911 corresponds to the direction of least shielding 011 with the highest frequency while 633 corresponds to the direction of highest shielding 033 with the lowest frequency The isotropic values digg OF Ciso are the average values of the principal components and correspond to the center of gravity of the line shape In many cases the spectrum or calculation will not depend on any given order and the values can be entered in any order However in some cases where the orientation of the tensors is also important 70 January 6
27. in ppm Reference SF The residual dipolar coupling is field dependent The value entered for d in the edit box is for the spec trometer frequency entered as reference frequency of the observed nucleus in MHz Spectra at dif ferent fields can be calculated from the same set of parameters based on different observe frequencies Coupled nuclei In the edit box enter parameters for each coupled nucleus on a separate line The parameters spin J and d should be separated by blank spaces To check for proper format use the Parse button to see the result of how WSolidslinterprets the input 61 January 6 2009 Chapter 3 Spin Systems Spin Nuclear spin of the coupled nucleus This parame ter is not affected by the state of the Tie to previous site flag J Indirect spin spin coupling constant in Hz d Residual dipolar coupling in Hz LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Parse Use this button to check if the parameters for the coupled nuclei have been entered correctly Background The quadrupolar interaction at a quadrupolar nucleus causes its axis of quantization to be tilted away from the direction of the external magnetic field This also modifies the spatial dependence of the dipo lar interaction so that magic angle spinning is not able to suppress the heteronucl
28. io cio eR a kh 34 202 Tablet Nuclear Properties lt s cons caa oa a ee ee eee en 35 233 PeriodieSystem of Elements oo 2 22 2222 ER nennen 37 2 34 Convalute gt 22 2 iaa a ba sa han ae wee wees bbe b as 37 23 Sale Speer 2 2 24 2 le be Be ew ee we ee Beas 37 236 Add Constant 2 222 24 ea War ER a VERA De eee dee eee eo ara i 37 22 7 Reverse Spectrum soii See Da ewe REE REGS aa 38 238 Absolute Value 22 2a 22 ER se a ee RR aan 38 24 Window Menu ou eee ee ee er ee er ee eee wee 39 25 Help Meni 3 on cetera ea Er a A EEE LE Be 40 2 6 Known Problems ociosos a a EEE RER RR 41 16 January 6 2009 Chapter 2 Menus The menu system of WSolids1 consists of the following pop up menus WSolids1 File Simulation Tools Window Help File p 18 File and document management Simulation p 24 Simulation models and parameters management Tools p 34 Calculational tools Window p 39 Multiple document management Help p 40 Help and program version information 17 January 6 2009 Chapter 2 Menus 2 1 File Menu The File pop up menu consists of the following items Er Simulation Tools Wit New window Open gt Save gt Exit New Window p 18 Opens a new spectrum window Open Spectrum p 18 Retrieves an experimental spectrum Save Spectrum p 22 Saves a spectrum Exit p 23 Exits WSolids1 2 1 1 New Window The New window item of the File p 18 pop up menu creates a new spectrum window in
29. is set in the Spectrum Default Parameter p 25 box Actually this value corresponds to the frequency of the chemical shift reference compound and is thus not SF or SFO1 as used in Bruker parameter files If an experimental spectrum is available this parameter is set by default and should not be changed 25 January 6 2009 Chapter 2 Menus This value is used in the conversion of ppm into Hz and vice versa For the direct observation of quadrupolar nuclei its magnitude relative to the quadrupolar coupling constant is important for the observed line shape Valid values for the Larmor frequency are any positive non zero floating point numbers Note All calculations assume that the Zeeman interaction is the dominant interaction high field approxi maton For example calculation of a Pake doublet with a dipolar coupling constant of 1 kHz and a spectrometer frequency of 100 Hz will not give the proper result The high field approximation is slightly relaxed in cases involving quadrupolar nuclei but one should always be aware of the approx imations behind any type of calculation Spectrum Size The spectrum size SI defines the size of the calculated spectrum in points and is set in the Spectrum Default Parameter p 25 box Traditionally its values are multiples of two but it is not limited to these numbers If an experimental spectrum is available this parameter is set by default Together with the high and low frequen
30. make sense to go to a higher field e Spin systems and spectra are allocated dynamically One may have as many spectra and spin sys tems as the memory resources of the computer allow In each case the spectrum and spin system parameters are filled with sensible default values This should allow for easy familiarization WSolids1 has no build in features to support iterative fitting In order to make the refinement of a calculated spectrum less painful a so called Cycle p 33 feature was implemented Depend ing on the context and the selected Cycle options pressing the Enter key will perform specific actions such as requesting spectrometer settings requesting spin system parameters requesting convolution parameters performing a calculation or switching to the next spectrum window e For several menu commands accelerator keys p 14 have been defined for example pressing C starts a calculation Also holding down the ALT key and pressing any character key activates the corresponding menu item edit control list box button etc for which the corresponding character is underlined Some of the description of features has already been formulated in the early nineties Nowadays with gigantic office software suites the user is certainly more accustomed to multiple documents etc but I guess it doesn t hurt to keep this description Also the look of WSolids1 is now archaic but remember Iam a one man company and not making any mone
31. menu consists of the following items WSolids1 File Simulation BESS Window Help Item Dipolar coupling constant Nuclear properties Periodic table Convolute Scale spectrum Add constant Reverse spectrum Absolute value Purpose Dipolar coupling con stant p 34 Nuclear properties p 35 Periodic table p 37 Convolute p 37 Scale spectrum p 37 Add constant p 37 Reverse spectrum p 38 Absolute value p 38 Invokes a dialog box to calculate dipolar coupling constants Displays a table of nuclear properties Displays a periodic system of elements relevant to NMR Performs an additional convolution of experimental or theoretical spectra Scale a spectrum by a given factor Adds the specified value to the intensity of the spec trum Reverses the frequency direction of the spectrum Generates the absolute value representation of the spectrum 2 3 1 Dipolar Coupling Constant Calculate Dipolar Coupling Constant Nucleus 1 Distance A X 1 000 H 1 Nucleus 2 Dipolar Coupling H 1 z 128123 453 Hz dem Me Selection of the Tools Dipolar coupling constant menu item invokes this dialog box To calculate the dipolar coupling constant follow these steps e Select from the two list boxes Nucleus 1 and Nucleus 2 the two nuclei constituting the spin pair use mouse arrow keys or first letter of nucleus e Enter the internuclear separation in An
32. natural abundancies of each isotope and tying the parameters of the sites together while the natural abundance parameter is set to 100 except for the passive site where this parameter should be zero e Or one could use two different sites The first site should correspond to coupling with one of the active cadmium isotopes say Cd 111 rel intensity 12 75 nat abund 100 The second site reflects both coupling to Cd 113 as well as the passive cadmium thus rel intensity 87 25 nat abund 14 05 because 14 05 of 87 25 corresponds to 12 26 in total Implementation Details For an introduction see for example the following reference and the literature quoted there in K Eichele R E Wasylishen J Magn Reson A 106 1994 46 56 Furthermore this article describes the technique of analyzing spectra using the dipolar splitting ratio method and outlines the background behind the program DSR This model employs the POWDER space tiling and interpolation procedure Figure 3 2 shows an example of the succesful simulation of a spectrum arising from the combined effect of chemical shift anisotropy and homonuclear dipolar coupling in a powder sample It is the PNMR spectrum of tetraethyl diphosphine disulfide shown as absorption and first derivative spectrum and the results have been published in K Eichele G Wu R E Wasylishen J F Britten Phosphorus 31 NMR Studies of Solid Tetraethyldiphosphine Disulfide A Rei
33. relevant to NMR By setting the magnetic field induction strength BO to a specific value in Tesla this dialog box calcu lates the corresponding Larmor frequency for the isotopes of the selected element The default value causes H 1 to have a Larmor frequency of 100 00 MHz The default value of the magnetic field is retrieved from the INI file and can be changed there If there is no INI file or no corresponding entry in the INI file the default value is 2 34867 T For information on the source of the nuclear data refer to Table of Nuclear Properties p 2 3 4 Convolute This option available from the Tools Convolute menu enables one to apply additional Convolution p 28 to experimental or calculated spectra For example if a calculation takes a long time it is advisable not to include any convolution into the calculation itself but to save the calculated spectrum to a file and apply convolution separately afterwards 2 3 5 Scale Spectrum This option available from the Tools Scale spectrum menu enables one to multiply a specific spec trum by a given factor For example if one exports a spectrum from WinNMR as ASCII file the spectrum may look jagged because WinNMR converts the intensities into integers and the spectrum did not take advantage of the full dynamic range This digitization loss can be circumvented by scaling the intensities up by some factor 2 3 6 Add Constant This option available fro
34. the MDI client area of WSolids1 A spectrum window is required to display experimental and calculated spectra All actions are usually performed for the currently active spectrum window For example retrieving a spectrum file from hard disk automatically replaces the experimental spectrum of the currently active spectrum window Some actions automatically generate a new window if they require a spectrum window in order to succeed and no active window exists For example retrieving a spectrum file will automatically load the spectrum into a new window if no window has the input focus However if a spectrum window has the focus WSolids1 will load and display the spectrum in this window 2 1 2 Open Spectrum The Open Spectrum item of the File p 18 pop up menu retrieves an experimental spectrum into the Spectrum Window p 18 having the focus If the currently active spectrum window already contains an experimental spectrum it is replaced by the new one If no active spectrum window exists a new spectrum window is created automatically Reading an experimental spectrum automatically changes the default parameters p 25 for the theo retical spectrum of course they can be modified afterwards Various formats of experimental spectra are automatically recognized by WSolids1 Please note that the file type option only determines which files are listed in the selection window and does not affect the way the selected file is treated WSo
35. their respective owners 4 3 Copyright Information Copyright C 1994 2007 Klaus Eichele All rights reserved This program executable help file and related files may be distributed freely and may be used without fee by any individual for non commercial use and by any government organization Although the copyright holder retains all rights to this document and the software package you are allowed to copy and distribute verbatim copies of them as you received them in any medium provided that you conspicuously and appropriately publish on each copy an appropriate copyright notice and disclaimer of warranty keep intact all the notices that refer to this license and to the absence of any warranty and distribute a copy of this license along with it This package may not be distributed as a part of any commercial package You are expressly not allowed to sell or license this package Inquiries about the use of this program or reports about problems may be directed via e mail to This information does not constitute any implied right of official support but within reasonable limits Iam willing to help users Klaus Eichele uni tuebingen de 4 4 Disclaimer of Warranty Because this software package is licensed free of charge there is no warranty to the extent per mitted by applicable law This package is provided as is without warranty of any kind either expressed or implied including but not limited to the implied warran
36. which allows for a greater variety of file formats Fixed another error in model MAS Spin 1 2 Spin S Diag p 58 cup 1 for sth 0 Modified processing in model MAS Spin 1 2 Spin S Shape p 64 Added Tools Scale spectrum p 37 to allow scaling of spectrum Modified enabling disabling of controls in convolution parameter box changed layout of dialog box 1 3 7 Version 1 16 Fixed cycle feature Actually not really fixed one problem created a new one Fixed MDI accelerators Processing modified for the following dialog boxes default parameters convolution parameters model selection static chemical shift anisotropy static dipolar chemical shift A2 AX static dipolar chemical shift AB static quadrupolar nucleus MAS chemical shift anisotropy HB MAS spin 1 2 spin S Diag About Open file Save file Edit sites Fixed errors in model Static Dipolar chemical shift A2 AX p 45 and VAS Dipolar chemical shift A2 AX p 66 for A2 system J is neglected now Fixed two errors in model MAS Spin 1 2 Spin S Diag p 58 sign error in sbsf term cet 1 for cth 1 Fixed update of BF1 in AQS file Fixed file handling functions to use WinAPI exclusively should allow to create and read more files 11 January 6 2009 Chapter 1 Getting Started 1 4 Multiple Document Interface MDI This topic provides some information about the Multiple Document Interface in general and its imple men
37. 1 or in matrix notation cose sing Rp sinp coso Z z 1 y Y X Now transferred to a three dimensional problem the goal will be to describe the coordinates in a final rotated system x y z which is related to some initial coordinate system X Y Z by the Euler angles The final system is developed in three steps each step involving a rotation described by one Euler angle At the start both coordinate systems X Y Z and x 1 y 1 z 1 shall be coincident 76 January 6 2009 Chapter 3 Spin Systems The first rotation involves the Euler angle a The x 1 y 1 z 1 axis system is rotated about the Z axis through an angle a counterclockwise relative to X Y Z to give the new system x 2 y 2 z 2 It is clear from the figure that this rotation mixes the coordinates along X and Y completely analogous to the two dimensional rotation described above while the coordinate along Z remains unaffected The rotation matrix to describe this operation is given by cos sing 0 Re sinx cosy 0 0 0 1 The second rotation involves the Euler angle The x 2 y 2 z 2 axis system is rotated about the y 2 axis through an angle counterclockwise to generate the new coordinate system x 3 y 3 z 3 Anal ogously to the first Euler rotation this mixes the coordinates along x 2 and z 2 while the coordinate along y 2 remains unaffected This operation also generates a line of nodes parallel to the direction of
38. 59 a DAS opn ly 2 Spies SUUKL o 20 OR REA Re EE OR AE EES OEE a A 61 381 Implementation Details 2 26624 eee ee ee a a ve ew ee 62 of MAS Spin 1 2 spines Shape 2 23 bres ads de HEH ee EE RS 64 3 10 VAS Dipolar Chemical ShM AZ AX gt 2225 2 ara RR nn 66 311 VAS DipolarChemidal Shit AB oscar a nungen 68 9 12 Spin System Parameters ne ke es 70 2121 REUS DICO ida Were eee eee ee Pee Ee Ye 70 22 IBAS PIEVIOUS EE da ir eee Basis Ea ee eee eee eee 70 Orbe ACORVORIMIOE lt Ge eo Ee ak Se ee a wR ee ee 70 3 124 btandatd Convention os cara Oa 22 82 ae nen Oa 70 3 123 Herteld Berger Conventio so cdo oe eee ee ar aa ek 71 312 6 Haeberlen Convenio coser dea an 71 3 12 7 Chemical Shift and Chemical Shielding c oooomoo oem 72 3422 Coupled To 0 pio had ee Seed oe eee ee Dee 73 2 129 Natural Abenden a ee ee Pe a 73 3 12 10 Dipolar Coupling Constant D 2 42 8 2a 2 ee ER ner einen 73 12 11 indirect Spin Spi Coupling Je ocios ua 28 aan en ee 73 3 12 12 Anisotropy in Indirect Spin Spin Coupling DeltaJ 74 SEI SE E E 2 2 aan en a ae En a OAN 74 3 12 14 Euler Angles eee ea bE ek ee ee ED EM ee Sa eee bs 75 2 42 19 ROMO ia o a III A ee nee 75 3 12 16 Theswivel Chait 2 4 6 e280 cares ess baad e CORY dee ee wae 78 4 12 17 Determimne Euler Angles 2 22020 be ga 20 a ee eS ae eR a 79 3 12 18 Electrie Field Gradient Tenkar a da zer ah Ee ee 79 3 12 19 Central Transition CT and Satellite Transitions ST
39. AS Dipolar chemical shift AB p 68 2 2 6 Edit Sites Edit Sites Static Static Selection Action Chemical shift anisotrop Chemical shift anisotropy Quadrupolar interaction up to second order for the observed nucleus including chemical shift anisotropy for a static powder sample Optionally dipolar and indirect coupling to a heteronucleus can be added note quadrupolar interaction if any is neglected for the coupled heteronucleus Spectrum of a powder sample spinning at the magic angle showing chemical shift anisotropy uses Herzfeld Berger tables Spectrum of central transition of a quadrupolar nu cleus in a powder sample spinning fast at the magic angle Considers spin spin interactions with a quadrupo lar nucleus under magic angle spinning using full matrix diagonalization Considers spin spin interactions with quadrupo lar nuclei under magic angle spinning using first order perturbation theory and stick approach Considers spin spin interactions with a quadrupo lar nucleus under magic angle spinning using first order perturbation theory to calculate line shape Considers chemical shift and spin spin interactions for a homo or heteronuclear pair of nuclei i e A2 or AX approximation under variable angle spinning Considers chemical shift and spin spin interactions for a homonuclear pair of nuclei i e AB approxi mation under variable angle spinning x ES CES The item Edit S
40. LB p 29 must be specified but can be different Note if calculations are performed in the frequency domain Lorentzian line shapes require considerably longer computation times because their wings extend much farther than those of Gaussian peaks For time domain convolution both line shapes require the same time This different behaviour arises from the fact that in the case of frequency domain convolution the subroutine uses a threshold value 0 00001 of the maximum intensity to reduce computation time Gaussian Convolution GB v Vo In the Convolution Parameters p 28 dialog box the value of GB in Hz specifies the full width at half maximum height of a Gaussian peak This line shape will be employed in the convolution of spectra The intensity at a given frequency is given by the following expression for an absorption mode Gaus sian 41n 2 v vo GB flv A exp where A peak maximum amplitude vo peak centre frequency GB full width at half maximum height In order to preserve the relative areas of sites with different line broadening parameters the con volution procedure takes into account that the area of a Gaussian peak can be approximated by vn 4ln2x A x GB 1 064467 x A x GB Lorentzian Convolution 29 January 6 2009 Chapter 2 Menus In the Convolution Parameters p 28 dialog box the value of LB in Hz specifies the full width at half max
41. P VAS NMR spectra of a molybdenum phosphine complex 69 January 6 2009 Chapter 3 Spin Systems 3 12 Spin System Parameters 3 12 1 Relative Intensity The relative intensity of each site determines the relative area this site contributes to the total line shape Allowed values are 0 100 but there is no check whether the relative intensities of all sites sum up to 100 Considered as a mere scaling factor To exclude a site momentarily from a calculation without deleting it set the relative intensity of this site to zero 3 12 2 Tie to previous site This feature allows to tie the parameters of a site to the parameters of the previous site using fixed factors Such a feature is useful if the spectrum is made up of a variety of different isotopomers and the site specific parameters differ only by ratios of nuclear constants Because such cases are rather rare the implementation here does not offer a high degree of sophistication There are a few points to keep in mind e More than one site needs to be available and this feature will not be available for the first site obviously e The simulation models for the sites tied together should be the same This is not checked Tying together different models may produce unexpected results e Once sites are tied together one cannot change the convention used for tensor components e Parameters not affected by the state of the Tie check box are grouped together with this check box
42. T Action Y Y Calculates the total spectrum consistin of central transition and satellite transitions IS Calculates spectrum only including the central transition Note that quadrupolar nuclei of integral spin don t have a central tran sition Y Calculates spectrum only including the satellite transitions ii This wouldn t calculate anything therefore the default action is to calculate the central transition 3 12 20 Spinning Frequency The spinning frequency is required in Hz Although the sense of rotation does not affect the spectrum valid values are limited to postivie numbers WSolids11 allows to have different spinning frequencies for different sites although this doesn t make sense physically This design flaw has been remedied in WSolids2 3 12 21 Speedy Calculation Some calculations are quite time consuming In such cases it is possible to select Speedy calculation in which case only 1 16 of the orientations will be included This is usually sufficient to reproduce the gross features of the line shape but this gain in speed is bought at the expense of accuracy In any case a final calculation with Speedy Calculation disabled should be performed to verify the parameters 80 January 6 2009 4 Acknowledgements Contents 41 Credits une oo we eS ia 81 4 2 Trademark Acknowledgements 1 0 eee ee ee 82 4 3 Copyright Information o ooo ooo ee ee ee ene 82 4 4 D
43. WSolids1 Solid State NMR Simulations USER MANUAL Klaus Eichele January 6 2009 2 January 6 2009 Contents 1 Getting Started 1 1 a 3 u 228 ee ae ea SES ES De ES POA EERE ee BAe LL11 sa da ooo are ea Mle dee ae ee Il RR AAN AE une na ho eo ee ee ea ee eth url 114 Trouble ew 22 4222 ee a ERs sn ee Re nenne A toe ae a ae ee ee Ee on he R 13 Bi ds o aive oe a ne au Bee a ee Led Version IIo 21206 2008 rer erraten Lad Version LIZO 25 05 2001 2 6 eck ne a a ee es 132 Venen Ll 20 2 CUB DD ee Be eR a RE E a 14 Version 17 22 07031999F o ec ee CREE eee A es Loa Werten WEI WI INT cons e ee Re Roe eS lee Verion LI ooe oe dit ee ee ei ea Ler PBN LIE oia amane a es a a Es ae ch ee e 1 4 Multiple Document Interface MDI 2 2 ooo 14 1 The Multiple Document Interface oa eo 2 easa ee 142 Menu Management oo esmerado sa anne an 143 Keyboard Intetiace o e ecne oe aae eR ee REE ew es La Bevbcard Acer oo oa eta beet hbo e ee eels Menus 21 DleMem soc ecepte ee node na ren ae Eee eRe KE ee en 2I New Winde ia ae nn an an an een 212 IPEN SPEEN na ern er EE en una 212 SAVE OPEL u eke be ee be RETR A Eee e ee RS Ea s DE MONG tor es ne to PG dee A Be oe eee Ey oS ee ee ees 22 Siler Med ends 22205 RR aras a ra Rae nah 22 1 Spectrum Default Parameters occa cc ee he ee ee aan 222 LOLA Parameters 05 3 4 bts am ans bak Bann e E 222 Derivative Mode o diro s ete e dt a m en a oe o A reat a EAS 22 5 Select Calew
44. and nuclear constants Mo Y rsl 3 p PA An 271 ris In contrast the indirect spin spin coupling p 73 between nuclear magnetic moments is mediated by intervening electrons 3 12 11 Indirect Spin Spin Coupling J The indirect spin spin coupling between the magnetic moments of nuclei is mediated by intervening electrons In contrast to the direct dipole dipole coupling p 73 there is no simple relationship between its magnitude and geometry In solution NMR studies the magnitude of this interaction 73 January 6 2009 Chapter 3 Spin Systems is simply called the spin spin coupling constant J reported in Hz In solid state NMR it is more adequately referred to as isotropic spin spin coupling constant as it is in principle anisotropic p 74 in nature 3 12 12 Anisotropy in Indirect Spin Spin Coupling Delta J The indirect spin spin coupling between the magnetic moments of nuclei is mediated by interven ing electrons This interaction is in principle anisotropic in nature Assuming axial symmetry the anisotropy of the indirect spin spin coupling is defined as the difference between the unique compo nent and the perpendicular components AJ Jy Ja In solution NMR spectra the anisotropy of the indirect spin spin coupling does not lead to split tings although it could provide a mechanism for relaxation Physically the anisotropy of the indirect spin spin coupling behaves exactly the same way as the direct
45. ation is used for labelling the axes of the EFG tensor VZZ gt VYY gt VXX Figure 3 7 shows an example for the succesful simulation of a MAS spectrum of a spin 1 2 nucleus that is coupled to a quadrupolar nucleus in a powder sample It is the C MAS NMR spectrum of a 59 January 6 2009 Chapter 3 Spin Systems chloroketosulfone where carbon is coupled to Cl 35 and Cl 37 and the results have been published in K Eichele R E Wasylishen J S Grossert A C Olivieri The Influence of Chlorine Carbon Dipolar and Indirect Spin Spin Interactions on High Resolution Carbon 13 NMR Spectra of Chloroketosulfones in the Solid State J Phys Chem 1995 99 10110 10113 This picture also illustrates the workings of the Tie to previous site feature the parameters of the C 13 C1 37 isotopomer are tied to those of the C 13 C1 35 isotopomer by using the ratios of the magne togyric ratios and nuclear quadrupole moments as factors 60 January 6 2009 Chapter 3 Spin Systems 3 8 MAS Spin 1 2 Spin S Stick MAS Spin 1 2 Coupled to Quadrupolar Nucleus Stick Site 2 ns Delta iso 0 000 Rel Intensity ULNA 100 000 _ Tie to previous site Balerence ai Spin y d 1 0 100 000 10 000 1 0 100 000 10 000 1 0 100 000 10 000 10101 Calculates the centerband i e high spinning frequency limit in the MAS spectrum of a powder sam ple containing a spin 1 2 nucleus spin spin couple
46. berlen y p s Beta 0 000 deg Nucleus A Nucleus B Anisotropy 108 500 ppm Anisotropy 62 000 ppm Alpha 109 000 deg Alpha 116 000 deg Beta 87 000 deg Beta 86 000 deg Gamma 191 000 deg Gamma 330 000 deg Figure 3 3 Experimental and calculated P NMR spectra of a static powder sample of tetraethyl diphosphine disulfide Background In addition to the chemical shift anisotropy CSA the spectrum of a spin pair will also depend on the direct dipolar coupling and potentially the indirect spin spin coupling between both nuclei Because both the CSA and dipolar interaction are tensorial interactions the actual line shape also depends on their relative orientation In contrast to the Az and AX first order spin systems the line shape of a general homonuclear AB spin system may also depend on the relative orientations of the two chemical shift tensors Implementation Details For an introduction see for example the following reference and the literature quoted there in K Eichele R E Wasylishen J Magn Reson A 106 1994 46 56 This model employs the POWDER space tiling and interpolation procedure Figure 3 3 shows an example of the succesful simulation of a spectrum arising from the combined ef fect of chemical shift anisotropy and homonuclear dipolar coupling in a powder sample It is the 31P NMR spectrum of pentacarbonyl molybdenum bis diphenylphosphino methane shown as absorp tion and first derivative spectrum a
47. clear electric quadrupole moment O in units of 10728 m frequency in MHz of the reference compound for that nucleus at the selected magnetic field strength Sorting By default the nuclei are listed according to their position in the periodic table of elements i e for increasing mass number Using the Sort for list box the display can be sorted alphabetically for the labels of the nuclei the spin the magnetogyric ratio Gamma the natural abundance or the nuclear electric quadrupole moment Magnetic Field The strength of the magnetic field affects the frequency of the reference compound The following values produce the given values of the H NMR frequency of TMS 36 January 6 2009 Chapter 2 Menus Bo T 1H frequency of TMS MHz 2 348661 100 00 4 700374 200 13 5 874703 250 13 7 049034 300 13 9 397695 400 13 11 746354 500 13 14 0950140 600 13 16 443674 700 13 18 792334 800 13 21 140994071 900 13 22 3153239 950 13 Copying Data Note that it is possible to high light parts of the table and to copy the highlighted parts to the clipboard using standard Windows editing techniques CTRL INSERT or CTRL C to copy the selected part Modifications Most nuclear data have originated from Mason s extremely useful book on Multinuclear NMR 1 The current version of R has been updated according to data from the IUPAC Recommendations 2001 6 The following data differ from those in reference 1 all magn
48. component of the electric field gradient EFG along a particular direction Vii egii The Laplace equation requires that the trace of the EFG tensor is zero In addition the EFG tensor is symmetric hence consists only of 5 independent components In its principal axis system PAS XYZ the EFG tensor is diagonal and can be characterized by the three principal components VXX VYY VZZ In nuclear quadrupole resonance NQR the principal components are labelled according to this convention VZZ gt VYY gt VXX Because of the trace of zero only two independent parameters are required to characterize the mag nitudes of the principal components and these are usually chosen to be VZZ and the dimensionless asymmetry parameter 7 The product of VZZ and the nuclear quadrupole moment is known as the quadrupolar coupling constant x Va O e 9 77 0 h h n Y Va FFY XX 37 ZZ Thus 7 is constrained to values between 0 and 1 The quadrupolar coupling constant should not be mixed up with the quadrupolar frequency observed in NOR experiments 79 January 6 2009 Chapter 3 Spin Systems 3 12 19 Central Transition CT and Satellite Transitions ST For a quadrupolar nucleus with a nuclear spin greater than 1 2 as observed nucleus one can select calculation of the central transition 1 2 gt 1 2 spectrum only CT of the satellite transition m m 1 with m 1 2 spectrum only ST or of all transitions CT S
49. ctra have been calculated Y In this case each site requires its own set of line broadening pa rameters Also the convolution routine is invoked each time af ter a site specific spectrum has been generated GB 200 GB 1000 27 January 6 2009 Chapter 2 Menus Note Although the convolution parameters belong to the spectrum window spec tra at different spectrometer frequencies will require different broadening the actual parameters are accessible via the spin system 2 2 2 Convolution Parameters Convolution Parameters Site independent convolution parameters GB LB 0 Gaussian GB LB 100 Lorentzian GB LB mixing 0 000 GB 50 000 Hz LB 50 000 Hz fS OF MESES The convolution parameters determine the amount of line broadening added to the calculated spec trum The convolution parameters should not be mixed up with the LB GB parameters used in apodization functions applied to experimental spectra Here they take into account the sum of all line broadening effects intrinsic to the sample and the spectrometer and processing Such effects can be inhomo geneity of the external magnetic field homonuclear dipolar couplings unresolved indirect couplings interactions with quadrupolar nuclei degree of crystallinity chemical shift dispersion insufficient decoupling power temperature gradients etc etc and finally the actual window function applied to the experimental
50. cy limits F1 p 26 and F2 p 26 the spectrum size deter mines the spectral resolution Often it is sufficient to use the same spectral resolution as the experi mental spectrum However in cases involving stick approaches a higher digital resolution for the calulated spectrum is advisable The spectrum size affects the time required for calculating a spectrum i e the performance of the interpolation routine for the powder averaging or the convolution routine depends on the digital res olution Valid values for the spectrum size are positive integers greater than or equal to 16 Additionally the letter K can be used to indicate Kilo points 1K 1024 points ppm Hz The two mutually exclusive radio buttons ppm and Hz in the Spectrum Default Parameter p 25 box allow to toggle the input between frequency Hz or chemical shift ppm units In order to perform the conversion the value presently selected for the spectrometer frequency p 25 is used Spectrum Limits F1 F2 150 100 50 0 50 100 150 ppm lt yv B The spectrum limits are specified by the high frequency limit in conventional NMR the left limit F1 and the low frequency limit F2 in the Spectrum Default Parameter p 25 box Dependent on the state of the radio buttons ppm Hz p 26 the input is taken in units of ppm or Hz To perform the conversion between ppm and Hz the current value of SF p 25 is taken In combi
51. d nucleus this is re quired to evaluate the Larmor frequency of the quadrupolar nu 3 2 Note For y 0 S can be 1 3 2 5 2 and 7 2 for y gt 0 S can be Note There can be a problem p 41 if the observed nucleus has a negative magnetogyric ratio Parameter Purpose Coupled to p 73 N A p 73 Tie to previous site p 70 Speedy calculation p 80 Delta iso p 70 Alpha p 74 Beta p 74 D p 73 J p 73 Delta J p 74 Chi p 79 Eta p 79 Specifies the quadrupolar nucleus the observed nu cleus is coupled to Only heteronuclear coupling will be considered Natural abundance in percent of the coupled nu cleus Ties parameters to those of the previous site If checked less crystallite orientations are included into the calculation Isotropic chemical shift in ppm Azimuth angle in degrees of the internuclear vec tor in the principal axis system of the electric field gradient tensor Polar angle in degrees of the internuclear vector in the principal axis system of the electric field gradi ent tensor Direct dipole dipole coupling constant in Hz Indirect spin spin coupling constant in Hz Anisotropy of the indirect spin spin coupling in Hz Quadrupolar coupling constant in MHz Asymmetry parameter of the electric field gradient tensor 0 lt eta lt 1 58 January 6 2009 Chapter 3 Spin Systems By Eile Simulation Tools Window Help l x
52. d to several heteronuclei typically quadrupolar nuclei Actually one could also calculate solution H 1 NMR spectra of gt 10 protons coupled to each other when the spectra are purely first order The break down of the high field approximation is taken into account using first order perturbation theory where the quadrupolar interaction is the per turbation Each coupling interaction can be described by an indirect spin spin coupling constant J and a field dependent residual dipolar coupling d as well as the number of nuclei coupled and their respective spins The program calculates the frequency of each transition and puts some intensity a stick into the corresponding bin of the spectrum array One may want to use a higher resolution for the calculated spectrum than for the experimental spectrum e g increase the number of points and decrease the spectral width as the center position of each peak is quantized according to the digital resolution Parameter Purpose Rel Intensity p 70 Relative intensity of this site in percent Tie to previous site p 70 Ties parameters to those of the previous site Ex cept for relative intensity and the spins of the cou pled nuclei all other parameters are affected by the setting of this flag Always have the site with the most coupled nuclei as first site followed by de creasing numbers Otherwise the result will be un predictable Delta iso p 70 Isotropic chemical shift
53. data In short the convolution parameters represent all these effects in a phenomeno logical manner Convolution is done in the frequency domain rather than in the time domain Exponential multi plication in time domain requires for N points N multiplications in contrast the equivalent in the frequency domain convolution with a Lorentzian peak requires N x N 1 multiplications unless a threshold value is specified Although considered part of the spectrum parameters rather than of the spin system access to convo lution parameters is gained by editing the spin system Convolution also depends on the setting of the site dependent convolution p 27 check box in the Spectrum Default Parameter p 25 box Parameter Purpose GB LB mixing p 29 The GB LB mixing in percent determines the amount of Gaussian Lorentzian character of the convolution function 0 pure Gaussian 100 pure Lorentzian GB p 29 Gaussian broadening in Hz LB p 29 Lorentzian broadening in Hz 28 January 6 2009 Chapter 2 Menus Gaussian Lorentzian Mixing In the Convolution Parameters p 28 dialog box the Gaussian Lorentzian mixing determines the weighting of Gaussian and Lorentzian line shapes in the convolution subroutine A value of 0 corresponds to a pure Gaussian line shape a value of 100 yields a pure Lorentzian line shape In the case of mixed line shapes both Gaussian broadening GB p 29 and Lorentzian broadening
54. e molecular frame of reference Implementation Details For an introduction see for example the following reference and the literature quoted there in K Eichele R E Wasylishen J Magn Reson A 106 1994 46 56 This model employs the POWDER space tiling and interpolation procedure Figure 3 1 shows an example of the succesful simulation of a spectrum arising from the chemical shift anisotropy of a powder sample It is the 91P NMR spectrum of a molybdenum phosphine complex and the results have been published in K Eichele R E Wasylishen K Maitra J H Nelson J F Britten Single Crystal 31P NMR and X ray Diffraction Study of a Molybdenum Phosphine Complex 5 Methyldibenzophosphole pentacarbonylmolybdenum 0 Inorg Chem 1997 36 3539 3544 44 January 6 2009 Chapter 3 Spin Systems 3 2 Static Dipolar Chemical Shift A2 AX Dipolar Chemical Shift A2 AX Site 2 Rel Intensity Convention 100 000 _ Tie to previous site Coupled to Si 29 hd 132 _ Homonuclear Spin 100 000 STANDARD M E 1650 000 0 000 Delta 11 Delta 22 Delta 33 Parameter 150 000 50 000 100 000 0 000 Delta J Alpha Beta ppm ppm ppm 72 000 98 000 Calculates the spectrum of a static powder sample containing an isolated spin pair considering chem ical shift anisotropy direct dipole dipole coupling and indirect spin spin coupling The spin pair can be a ho
55. e daa a eee wee eee wea wad ad 21 ESMAS geo oe So a ae Be Bee Bates Rae Beek af Sn eee ye eee Be a 21 DIMPS e woe eee ea eA a AR eee eee wee eS 22 WTA eek a a Ss boa ds Be deed ead a ge BOR Ee GE ERE BOR oe ak oe ii 22 PAS Save Speer pogi Ge Dida na ie i be aeg et 22 2 BRI ce ey te ee EL ee PK eek cee hed ee eee Hoe ee i nta eh 23 22 Simulation MENU i s ik ka ana ana rn nr nn ew eee 24 221 Spectrum Default Parameters 2 2 2 2 5 ca ze ee ia 25 Observed Nucleus 2 2222 CC Coon 25 Spectrometer Fregiieneg lt o ca 22a dot a ke eR RG bas 25 es o o ae Gate a Paw a Ba a ehe 26 PRESEA EES ESET EA das 26 Spectruert Lie oa 0 be ek hei hee hbo eee eee ew a b A 26 Use Relative Threshold Value ee ee 27 Site Dependent Broadening A 27 2 22 Convolution Parameters c co co 640464654 Seren een nn 28 Gaussian Lorentzian Ming cs ce 22 8 as 29 Gaussian Convolution ee a a a 29 Lorentzian Convolution 66 s es ece s ee ee eS 29 223 Derivative Mode 2 2 4 0020 ea ea ae we da we eee we 30 224 NEW SHE rocade RG A Bek ele et Pk eh oe wl a a Ba wh a Sw a a 31 22 5 Select Calculation Model 2 2 2 2 44 4444 Sana Se ba ee aaa 31 o ok ok ek OE ek Re RO OREN Uh le Sh let GG ale ac ee uas 32 der MCUs es hee he kh ewe eae wae be tedoetawe dada des 33 De A 33 A A o a aaa Ses a aa Da eae ae 33 22 0 Cycle Bronson Sa Paws EE aaa inet 33 Chapter 2 Menus 23 Tools Men 6 64 6468 64 KHER SHH DE DH nn re 34 231 DipolarCoupling Constant
56. e heteronuclear dipolar coupling in the spectrum of the spin 1 2 nucleus resulting in splittings and broadenings Similar effects can be transmitted through the indirect spin spin coupling If the nuclear quadrupolar coupling constant is on the same order of magnitude as the Larmor frequency of the quadrupolar nucleus the combined Zeeman quadrupolar Hamiltonian must be diagonalized at each orientation and averaged over a rotor period to calculate a theoretical spectrum However if the quadrupolar coupling is relatively small this so called breakdown of the high field approximation causes lineshapes that can be simulated us ing first order perturbation theory If the broadening is small such lineshapes can also be analyzed 64 January 6 2009 Chapter 3 Spin Systems iol x E Eile Simulation Tools Window Help lal x ste sae O ens Suc 0 taeen yy Coupled to Spin 1 N _ Re to previous site Delta iso ppm D Hz Mona wg he Beta D deg Delta J Hz ci Me Ei Figure 3 9 Experimental and calculated C MAS NMR spectra showing coupling to N using a stick approach Figure 3 9 shows an example for the succesful simulation of a MAS spectrum of a spin 1 2 nucleus that is coupled to several quadrupolar nuclei in a powder sample It is the 13C MAS NMR spectrum of NH4 SeCN where carbon is coupled to a N 14 nucleus and the results have been published in G M Bernard K Eichele G Wu C
57. ear dipolar coupling in the spectrum of the spin 1 2 nucleus resulting in splittings and broadenings Similar effects can be transmitted through the indirect spin spin coupling If the nuclear quadrupolar coupling constant is on the same order of magnitude as the Larmor frequency of the quadrupolar nucleus the combined Zeeman quadrupolar Hamiltonian must be diagonalized at each orientation and averaged over a ro tor period to calculate a theoretical spectrum However if the quadrupolar and dipolar coupling are small relative to the indirect spin spin coupling this so called breakdown of the high field approxi mation causes no significant broadening of the individual peaks only unequal spacings between the peaks of the multiplet Such spectra can be simulated using first order perturbation theory with a stick approach where the patterns are characterized by an indirect spin spin coupling constant J and a residual dipolar coupling d 3 8 1 Implementation Details The theory behind this model is outlined in e A C Olivieri J Magn Reson 1989 81 201 205 e R K Harris A C Olivieri Progr NMR Spectrosc 1992 24 435 456 e An introduction into applications with several examples is also given in K Eichele R E Wasylishen Inorg Chem 1994 33 2766 2773 Figure 3 8 shows an example for the succesful simulation of a MAS spectrum of a spin 1 2 nucleus that is coupled to several quadrupolar nuclei in a powder sample It is the 113Cd
58. eem to assume that the three fixed axis rotations have to be one each around X Y and Z Not true I find that a much more intuitive set of Euler angles is produced by using the Z Y Z choice of axes Z X Z is very similar Let me illustrate Most of you are reading this sitting in a chair at a desk Let s assemble a completely general rotation allowing you to point at any place on the floor walls or ceiling 2 degrees of freedom with any tilt to your head 1 degree of freedom Global coordinate system Z is up X is front to back pointing towards you Y is left to right This system will stay attached to your desk as you move Rotation 1 About the Z axis Turn your chair so that the chosen point is ahead of you It may still be up on the ceiling or down on the floor but it should be in the plane of symmetry of your body A swivel chair is great to have here First intermediate coordinate system Z is still up because we rotated around Z X is your new front to back you left the global X attached to the desk Y is your new left to right attached to the arms of your chair Rotation 2 About the Y axis Tilt forward or backward until your head is pointing at the chosen point Ignore the strange looks from your office mates Second intermediate coordinate system Z comes out of the top of your head Y is the same as it was in the previous first intermediate coordinate system because we rotated around Y X is no longer
59. ems 3 6 MAS Quadrupolar Nucleus MAS Quadrupolar Nucleus 2nd order Site 6 Rel Intensity LUURI _ Tie to previous site Chi 0 120 Eta 0 000 Delta iso 0 000 Coupled to B 11 X Spin 3 2 N 100 000 J 0 000 Calculates powder MAS spectrum of the central transition of a quadrupolar nucleus considering the quadrupolar interaction to second order Additionally indirect coupling to a heteronucleus can be added note quadrupolar interaction if any is neglected for the coupled heteronucleus Parameter Purpose Rel Intensity p 70 Relative intensity of this site in percent Tie to previous site p 70 Ties parameters to those of the previous site Delta iso p 70 Isotropic chemical shift in ppm Chi p 79 Quadrupolar coupling constant in MHz Eta p 79 Asymmetry parameter of the electric field gradient tensor 0 lt eta lt 1 Coupled to p 73 Specifies the nucleus the observed nucleus is cou pled to Only heteronuclear coupling will be con sidered N A p 73 Natural abundance in percent of the coupled nu cleus If smaller than 100 WSolids1 automatically includes calculation of the spectrum of the uncou pled spin species J p 73 Indirect spin spin coupling constant in Hz LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters
60. ers used Parameter Purpose Coupled to p 73 Specifies the quadrupolar nucleus the observed nu cleus is coupled to Only heteronuclear coupling will be considered N A p 73 Natural abundance in percent of the coupled nu cleus Tie to previous site p 70 Ties parameters to those of the previous site Delta iso p 70 Isotropic chemical shift in ppm Alpha p 74 Azimuth angle in degrees of the internuclear vec tor in the principal axis system of the electric field gradient tensor Beta p 74 Polar angle in degrees of the internuclear vector in the principal axis system of the electric field gradi ent tensor Dip 73 Direct dipole dipole coupling constant in Hz Jip 73 Indirect spin spin coupling constant in Hz Delta J p 74 Anisotropy of the indirect spin spin coupling in Hz Chi p 79 Quadrupolar coupling constant in MHz Eta p 79 Asymmetry parameter of the electric field gradient tensor 0 lt eta lt 1 LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Background The quadrupolar interaction at a quadrupolar nucleus causes its axis of quantization to be tilted away from the direction of the external magnetic field This also modifies the spatial dependence of the dipo lar interaction so that magic angle spinning is not able to suppress th
61. etermined more accurately As indicated in the picture 30 January 6 2009 Chapter 2 Menus the points of inflection e g 911 and 633 correspond to peaks in the first derivative while the discon tinuities e g 622 reveal themselves as peaks in the second derivative The width of the peaks in the first derivative line shape indicates the natural line width a parameter which can be employed in the convolution of the calculated spectrum References e T G Oas C J Hartzell T J McMahon G P Drobny F W Dahlquist J Am Chem Soc 1987 109 5956 e T G Oas C J Hartzell F W Dahlquist G P Drobny J Am Chem Soc 1987 109 5962 e C J Hartzell M Whitfield T G Oas G P Drobny J Am Chem Soc 1987 109 5966 2 2 4 New Site A site is an independent part of a spectrum with a line shape uniquely defined by parameters e g chemical shifts couplings etc specific to the calculational model selected for this site The feature New Site of the Simulation p 24 popup menu adds a new site to the calculation model It calls the Select Calculation Model p 31 dialog box and requests the user to select a model After wards it initiates the input of the appropriate site specific parameters 2 2 5 Select Calculation Model Select Calculation Model ic Chemical shift anisotrop ic Dipolar chemical shift 2 AX ic Dipolar chemical shift AB ic Quadrupolar nucleus Chemical shift anisotropy
62. etogyric ratios are according to 6 e the nuclear quadrupole moment values are from the Year 2001 Q Values collected by Pekka Pyykk 3 e the dedo ratios of Sn 119 and Sn 117 could be 3 less than the accepted value 2 i e 9 997559 x 107 rad s T and 9 552955 x 107 rad s T instead of 10 021x107 rad s T and 9 589x 10 rad s71 T71 e Nd 145 apparently has a spin of 7 2 instead of 5 2 4 5 Similarly U 235 has a spin of 7 2 instead of 5 2 4 5 U 233 has been added to the tables 4 5 References 1 Joan Mason Multinuclear NMR Plenum Press New York 1987 2 A Laaksonen and R Wasylishen J Am Chem Soc 1995 117 392 400 3 P Pyykk Mol Phys 2001 99 1617 1629 4 Quantities Units and Symbols in Physical Chemistry IUPAC 5 CRC Handbook of Chemistry and Physics 6 R K Harris E D Becker S M Cabral de Menezes R Goodfellow P Granger Solid State Nucl Magn Reson 2002 22 458 483 37 January 6 2009 Chapter 2 Menus 2 3 3 Periodic System of Elements Periodic System of Elements Nane Hydrogen 2 1 Magnetic Field T Isotope H 1 H 3 N A 99 988 E 8 998 Spin 1 2 1 2 SF MHz 400 135 x 426 799 ORBOGEODGDEDGENDE Ba ta me ta w rojos v eaula e es ro ar en This dialog box accessible from the Tools Periodic table menu item displays a periodic system of elements with information
63. ges from 1 0 for spinning parallel to the field to 0 5 for spinning perpendicular to the magnetic field Figure 3 10 shows an example for the succesful simulation of a spectrum arising from the combined effect of chemical shift anisotropy and heteronuclear indirect and dipolar coupling in a powder sample under fast variable angle spinning It is the 31P NMR spectrum of a cadmium phosphine complex 66 January 6 2009 Chapter 3 Spin Systems VAS Dipolar Chemical Shift Spin Pair 100 000 STANDARD 65 380 mo 340 000 000 000 000 Figure 3 10 Experimental and calculated P VAS NMR spectra of a cadmium phosphine complex 67 January 6 2009 Chapter 3 Spin Systems 3 11 VAS Dipolar Chemical Shift AB VAS Homonuclear Two Spin System AB 1500 000 60 000 Site 3 D J Rel Intensity LUU _ Tie to previous site Delta J 0 000 Convention STANDARD Alpha 10 000 VAS angle 60 000 deg Pete 40 000 Nucleus A Nucleus B Delta 11 100 000 ppm Delta 11 100 000 Delta 22 50 000 ppm Delta 22 50 000 Delta 33 100 000 ppm Delta33 100 00 Alpha 0 000 deg Alpha 0 000 Beta 20 0 deg Beta 20 000 Gamma 0 000 80S deg Gamma 0 000 Spectrum of a powder sample under variable angle spinning containing a homonuclear spin pair using AB equation Background In addition to the chemical shift anisotropy CSA the spectru
64. gstrom e Hit Enter to display the calculated dipolar coupling constant 35 January 6 2009 Chapter 2 Menus If required copy the result to the clipboard by pushing the Copy button or ALT O This can be used to paste typically CTRL V or SHIFT INSERT the result into appropriate edit controls Exit the dialog by selecting Quit or ESC For information on the source of the nuclear data refer to Table of Nuclear Properties p 35 2 3 2 Table of Nuclear Properties Nuclear Properties o 100300042 0NA Nucleus Spin Gamma 1E07 N A Q 1E 28 Frequency H 1 122 26 75221 99 9880 00000 950 1301 H 2 E 4 10663 BULLS 00286 145 8508 H 3 172 28 53498 0000 00000 1013 4466 He 3 172 20 38016 0001 00000 723 8206 Li 6 a 3 93717 5900 00081 139 8323 Li 7 372 10 39770 4100 04010 369 2841 Be 9 372 3 759567 0000 05288 133 5281 B 10 3 87468 9000 0 08459 102 0969 B 11 372 58470 5 04059 304 c 13 172 72828 5 00000 238 N 14 1 93378 02044 68 N 15 172 71262 00000 96 0 17 572 62808 0 02558 128 F 19 172 18148 E 00000 894 Ne 21 342 11308 5 10155 75 Sort for No v Magnetic Field T 22 3153 Me 2 This dialog box accessible from the Tools Nuclear properties menu item lists nuclear properties for many of the known NMR active nuclei The Properties nuclear spin quantum number magnetogyric ratio Gamma in units of 107 rad s T natural abundance N A in nu
65. ic spline interpolation and Marquardt Levenberg non linear least squares procedures are adopted and adapted from W H Press S A Teukolsky W T Vetterling B P Flannery Numerical Recipes in C Cambridge University Press Cambridge 1992 Microsoft for providing Visual C 2008 Express Edition for free Jordan Russell for making Inno Setup available http www jrsoftware org Jochen Kalmbach for demonstrating how to statically link against the Microsoft CRT and thus get rid of VCREDIST_X86 EXE http blog kalmbach software de Chapter 4 Acknowledgements e chicks for demonstrating in his pdfp PDF tools how to establish Dynamic Data Exchange DDE with Adobe Acrobat Reader http www esnips com web PDFTools e This manual has been produced using the MiKTEX http www miktex org distribution of TATFX in combination with the TeXnicCenter editor http www ToolsCenter org 4 2 Trademark Acknowledgements Microsoft MS is a registered trademark and MS DOS MS Word and MS Windows are trade marks of Microsoft Corporation WordPerfect and WordPerfect Presentations were products of WordPerfect Corporation intermit tently by Novell now by Corel WIN NMR is a product of Bruker Franzen Analytik GmbH Spinsight is a product of Chemagnetics Hewlett Packard Company HPGL Other brand and or product names are used for identification purposes only and are trade marks registered trademarks or copyrights of
66. ids1 as a generic WINNMR file the data files need to adhere to the following format where eee stands for the three digit experiment number and ppp for the three digit processing number each zero padded if necessary Thus an experiment number of 2 and a processing number of 1 would result in the file name 002001 WSolids1 itself doesn t care about the eeeppp format e eeeppp 1R or eeeppp FID in binary floating point format need to be present currently WSolids1 does not read FID s e eeeppp AQS and eeeppp FQS need to be present in the same directory these parameter files are in binary format of fixed record length and start with A000 the AQS file contains the parameters SFO1 SW_h Ol and FOS contains SR Bruker WINNMR UNIX This file format is similar to the generic WIN NMR p 20 file format however the parameter files are of ASCII type and correspond to those generated by UXNMR and XWin NMR WSolids1 uses this file format itself to store calculated spectra In order to be recognized by WSolids as UNIX type WINNMR file the data files need to adhere to the following format e eeeppp 1R or eeeppp FID in binary floating point format need to be present Note that generic UXNMR files have these data stored as long integers potentially if coming from an SGI the Endianness could also be different If such a file is read WSolids1 attempts to detect and convert them automatically currently WSolids1 does not read FID s e eeepp
67. imum height of a Lorentzian peak This line shape will be employed in the convolution of spectra The intensity at a given frequency is given by the following expression for an absorption mode Lorentzian A i fo where A peak maximum amplitude vo peak centre frequency LB full width at half maximum height In order to preserve the relative areas of sites with different line broadening parameters the con volution procedure takes into account that the area of a Lorentzian peak can be approximated by 7 2 x A x LB 1 570796 x A x LB 2 2 3 Derivative Mode In the Spectrum Default Parameter p 25 box the status of the mutually exclusive radio buttons Derivative No 1st 2nd determine whether the calculated spectrum will be displayed in normal ab sorption mode or as the first or second derivative Note The experimental spectrum remains unaffected by this setting Use your favourite NMR processing program to manipulate the experimen tal spectrum Taking the derivative of a spectrum dramatically de creases the signal to noise ratio Modern processing software has usu ally some sort of digital filtering e g Savitzky Golay implemented for generating derivatives of spectra For calculated spectra one can get away with a much simpler procedure 0 There are certain advantages in fitting the line shape in one of the derivative modes In this mode the frequencies of the singularities can be d
68. in the workspace of the frame window When maximized document windows are sized to fill the entire workspace of the frame window not the entire Windows desktop The title bar of a maximized document window disappears and its caption text is appended to the caption text in the frame window s title bar In addition the system menu bitmap of the document window becomes the first item in the menu bar of the frame window and the button to restore the document window to normal size is positioned at the far right of the frame window s menu bar 1 4 2 Menu Management The frame window s menu bar has a popup menu bar item called Window near the right end of the menu just left of the Help item The Window popup menu contains items related to the arrangement of document windows within the workspace These options include tiling and cascading of windows and arranging icons at the bottom of the workspace 12 January 6 2009 Chapter 1 Getting Started 1 4 3 Keyboard Interface The Windows MDI has its own keyboard interface that augments the keyboard interface for non MDI applications The MDI key sequences allow users to easily navigate between and manipulate docu ment windows within an MDI application just as they can navigate between and manipulate applica tions on the Windows desktop see also the section on keyboard accelerators p 14 in WSolids1 e CTRL F4 closes the currently active document window ALT F4 closes an applicatio
69. ion 1 17 21 09 10 1998 e Changed the meaning of SF p 25 spectrometer frequency this parameter corresponds now to the frequency of the chemical shift standard e Fixed a bug in model MAS Spin 1 2 Spin S Stick p 61 the factor dealing with reference SF and different Larmor frequencies worked in the opposite sense of the intended direction 10 January 6 2009 Chapter 1 Getting Started Added Tools Add constant p 37 to allow for a very simple baseline correction Added Tools Absolute value p 38 to generate the absolute value representation Added Tools Reverse spectrum p 38 to reverse the sense of a spectrum Problems with the cycle feature p 33 got probably fixed now Introduced an option in the convolution of spectra to switch off the use of a threshold value p 27 Different sites calculated with the model MAS Chemical Shift Anisotropy HB p 53 should have the proper relative intensities now Added functions to read experimental spectra in Chemagnetics SpinSight p 21 format Added functions to read WinNMR ASCII p 20 spectra directly without the need to convert them into SOLIDS format 1 3 6 Version 1 17 Added a new calculation model MAS Quadrupolar nucleus p 56 Fixed a memory problem bug in model MAS Spin 1 2 Spin S Stick p 61 and modified processing Changed the handling of spectrum files WSolids1 now uses the NMRFILES dynamic link library developed for WSolids2
70. is described in topic Determining Euler Angles p 79 The usual ranges for Alpha Beta and Gamma are 0 lt Alpha lt 360 0 lt Beta lt 180 0 lt Gamma lt 360 References 1 G Arfken Mathematical Methods for Physicists 3rd ed Academic Press New York 1985 2 M E Rose Elementary Theory of Angular Momentum Wiley New York 1957 3 K Schmidt Rohr and H W Spiess Multidimensional Solid State NMR and Polymers Academic Press London 1994 3 12 15 Rotation Matrices Rotations or transformations from one coordinate system into another are conveniently described by the triplet of Euler angles p 75 a p y Using the Euler angles this three dimensional problem can 75 January 6 2009 Chapter 3 Spin Systems be dissected into a sequence of two dimensional rotations whereby in each rotation one axis remains invariant Here all rotations are counter clockwise right handed mathematically positive sense In order to simplify the problem let us start with a two dimensional rotation Suppose the coordinates x y of a point in the two dimensional XY system are known but we are actually interested in knowing the coordinates of this point in another coordinate system X Y which is related to the XY system by a counter clockwise rotation by an angle As the figure indicates the coordinates of the given point in the new coordinate system will be xcosp ysing xsing ycosp 3
71. isclaimer of Warranty o ooooooo ee ee ee ee ene 82 4 1 Credits Some of the early FORTRAN modules were written by William P Power dipolar chemical shift NMR quadrupolar powder patterns QUADPOW and SECQUAD Gang Wu dipolar chemical shift NMR of homonuclear spin pairs This program contains for space tiling and interpolation purposes the POWDER routine We are grateful to D W Alderman for a copy of the routine in FORTRAN D W Alderman M S Solum D M Grant J Chem Phys 1986 84 3717 We learned a lot from A C Olivieri s BASIC program ANYCHI to calculate the MAS spectrum of a spin 1 2 nucleus coupled to a spin 3 2 nucleus S H Alarcon A C Olivieri R K Harris Solid State Nucl Magn Reson 1993 2 325 We are grateful to Alejandro C Olivieri for making his program available The design of WSolids1 received some ideas gained by working with the program ANTIOPE We are grateful to John S Waugh for making a copy of this program available to us F S de Bouregas J S Waugh J Magn Reson 1992 96 280 Thanks are due to Jim Frye and Glenn Sullivan both Chemagnetics Varian NMR for their help with the implementation of the SpinSight file import We are grateful to Dr Hans Forster Bruker for providing information on the WinNMR format We acknowledge the notes by W M Westler and F Abildgaard posted on the internet on DMX Digital Filters and Non Bruker Offline Processing The algorithms for bicub
72. ites of the Simulation p 24 popup menu allows to manage the sites constituting the calculational model A dialog box provides a list of currently available sites Edit Highlight the desired site in the list box using mouse or keyboard and select the Edit button to obtain access to the parameters for this site You can also double click on the desired site to trigger this action 32 January 6 2009 Chapter 2 Menus Add Select the Add button to add a new site to the calculational model Delete Select the Delete button to delete the site highlighted in the list box A dialog box requesting confirmation pops up before the site gets actually deleted There is no Undo function Note Access to editing the parameters of a spin system might be easier by using the cycle p 33 feature i e hitting the Enter key the appropriate number of times 2 2 7 Calculate The item Calculate of the Simulation p 24 popup menu starts calculation of a theoretical spec trum using the selected calculation models and site specific parameters If not all parameters were initialized it calls the appropriate parameter dialog boxes After a successful calculation the calcu lated spectrum will be displayed If there is no spectrum window currently active this procedure also opens a spectrum window and asks for default spectrum parameters The detailed calculation mode depends on the state of the Active only p 33 menu item
73. ive intensities scal ing mode of the dual multiple display window 22 January 6 2009 Chapter 2 Menus 2 1 4 Exit The Exit item of the File p 18 pop up menu quits WSolids1 All existing data will be lost if not saved prior to selecting Exit 23 January 6 2009 Chapter 2 Menus 2 2 Simulation Menu The Simulation pop up menu consists of the following items WSolids1 Sea Tools Window Help Default parameters New site Edit sites Calculate v Active window only Cycle through Enter Cycle options Item Purpose Default parameters p Invokes a dialog box to retrieve parameters for the 25 calculated spectrum New site p 31 Allocates and adds a new site to the calculational model Edit sites p 32 Manage sites modify parameters etc Calculate p 33 Performs a calculation using the currently selected simulation models and parameters Active window only p Perform calculation for currently active spectrum 33 window only or for all spectrum windows Cycle through p 33 Calls the next step in the Input Calculate Display cycle Cycle options p 33 Customize the cycle steps 24 January 6 2009 Chapter 2 Menus 2 2 1 Spectrum Default Parameters The Default parameters item of the Simulation p 24 popup menu invokes the Spectrum Default Parameters dialog box The default parameters characterize the appearance of the calculated spectrum they apply to
74. lation Medel 2 2 4 2884 bead ee bee ernten De ee ee A PR ER Be Re ee oS Bee er 227 Caledlate 244 oh ee badass eee Sede neh aan 228 Ale occ cb eee va e OE Re ee ee hee ee a eo 223 CMOS o cor ar De ease bee ana ner ZEN A re ew a ee ee a Bes NG RN co tine oe a ee ARES 20 Dipolar Coupling Conslant s s socs tetette rra i bey ee ee ee Ys 20 2 Table pl Nuclear Properties noch ba anne BRO oe a 20 0 Periodic System of Blements 0 62 6 6644 220 eb awe REO ee HEH a 224 TOWolle 0 ee donaa a A er Bd PO HT cos Dile he es nn een aia oe N Zap Add COSINE e poese hla re nennen a Zot Reverse SPRCHE II ann 232 ALGO Valle os cyo rora mie tebii Ee a 24 Window Men ce ana heka g k uae ee es Contents 20 ICIS srece AAA 40 29 Kroni Problems u a og ee oe Ge eh ee a en 41 3 Spin Systems 43 3 1 Static Chemical Shift Anisotropy e c so ca soe wen nenne un ran we 43 3 2 Static Dipolar Chemical SH HEIZ AX 6 4 6 eas sesi eee nee ana 45 33 Static Dipolar Chemical Shift AB 2 a 44 4088 sae cee See eee eee 48 3 4 Static Quadrupolar Nucleus co roe poe ae nee 50 om Implementation Delle conos be eae ee Se OR a 51 Dae o EAN 52 35 MAS Chemical Shit Anisotropy HB e p lt sa ba mS 53 3 6 MAS Quadrupolar Nucleus 24606 644006 ba e a ewe 56 al Implementation Delle ocu 56 352 Referencias Pa Ben nern har ee 57 37 MAS Spin 1 2 Spied Diag os escenas ne nam ner na 58 ad implementation Details coccion eee an
75. lids1 will always rely on its own strategy to determine the file type Thus in order to be recognized the spectrum needs to follow a certain pattern as detailed below for each file format 18 January 6 2009 Chapter 2 Menus These are the file formats recognized by WSolids Spectrum format Characteristics TopSpin XWinNMR p 19 Requires an 1r file in floating point or integer for mat and the parameter files acqus and procs in JCAMP DX format WINNMR generic p 20 Requires an 1R or FID file in floating point format and the parameter files aqs and fqs in binary for mat WINNMR UNIX p 20 Requires an 1R or FID file in floating point format and the parameter files AQS and FOS in ASCII for mat WINNMR ASCI p 20 Reads a spectrum file in ASCII format generated by Bruker s WinNMR version 5 1 or later it requires a single file usually with the extension TXT Spinsight p 21 Reads a Chemagnetics Spinsight file SOLIDS p 21 requires an ASCII file with header followed by in tensity data preferred extension dat JCAMP DX p 21 requires an ASCII file that follows the JCAMP DX standard preferred extension dx Simpson p 22 Varian p 22 Bruker TopSpin XWinNMR Spectra stored in Bruker s TopSpin or XWinNMR file format consist of a series of files stored in a convoluted directory structure as indicated in this figure user directory e g C u e g e g e g e g
76. m of a spin pair will also depend on the direct dipolar coupling and potentially the indirect spin spin coupling between both nuclei Because both the CSA and dipolar interaction are tensorial interactions the actual line shape also depends on their relative orientation Spinning the powder sample rapidly about an axis that forms an angle different from the magic angle with respect to the external magnetic field the resulting lineshape will look like that of a static powder sample but scaled by a factor that depends on the spinning angle This scaling factor ranges from 1 0 for spinning parallel to the field to 0 5 for spinning perpendicular to the magnetic field Figure 3 11 shows an example for the succesful simulation of a spectrum arising from the combined effect of chemical shift anisotropy and homonuclear indirect and dipolar coupling in a powder sample under fast variable angle spinning It is the 31P NMR spectrum of fac OC 3 h2 phen Mo h1 Ph2P PPh2 and the results have been published in K Eichele G Ossenkamp R E Wasylishen T S Cameron J F Britten Phosphorus 31 Solid State NMR Studies of Homonuclear Spin Pairs in Molybdenum Phosphine Com plexes Single Crystal Dipolar Chemical Shift Rotational Resonance and 2D Spin Echo NMR Experi ments Inorg Chem 1999 38 639 651 68 January 6 2009 Chapter 3 Spin Systems VAS Homonuclear Two Spin System AB Figure 3 11 Experimental and calculated
77. m the Tools Add constant menu enables one to add a constant value to an existing spectrum basically a constant base line correction 38 January 6 2009 Chapter 2 Menus 2 3 7 Reverse Spectrum This option available from the Tools Reverse spectrum menu enables one to reverse the frequency direction of the spectrum Physically for a spectrum consisting of n points this exchanges the intensity of the first and n th point the second and n 1 th point and so on Some versions of WinNMR do not provide such a functionality to swap the high and low frequency halves of the spectrum although some Bruker spectrometers produce d spectra for which this is was necessary 2 3 8 Absolute Value This option available from the Tools Absolute value menu enables one to generate the absolute value representation of the spectrum 39 January 6 2009 Chapter 2 Menus 2 4 Window Menu The Window menu allows management of spectrum windows and select display regions It consists of the following items WSolids1 File Simulation Tools BiS Expand spectrum Ctrl gt Compress spectrum Ctrl lt Multiply Ctrl Up rrow Divide Ctrl Down rrow Reset display Ctrl R Cascade Tile Arrange Icons Close All Item Action Expand spectrum Horizontally expand spectra frequency scale in the currently active spectrum window Compress spectrum Horizontally contract spectra frequency scale in the currently active spectr
78. magic angle spinning will depend on the spinning frequency if the spinning frequency is lower than the width of the chemical shift powder pattern In this case the isotropic peak center peak is flanked by spinning sidebands spaced at integer multiples of the spinning rate The intensities of the spinning sidebands are intimately related to the principal components of the chemical shift tensor For efficiency reasons WSolids uses look up tables of precomputed spinning sideband intensities Figure 3 5 shows an example for the succesful simulation of a spectrum arising from chemical shift anisotropy in a powder sample under magic angle spinning It is the 31P CP MAS NMR spectrum of a phosphinidene ruthenium cluster nido Ru4 CO 13 m3 PPh and the results have been published in K Eichele R E Wasylishen J F Corrigan N J Taylor A J Carty Phosphorus 31 Chemical Shift Tensors of Phosphinidene Ligands in Ruthenium Carbonyl Cluster 53 January 6 2009 Chapter 3 Spin Systems Chemical Shift Anisotropy STANDARD 889 000 294 000 60 000 i TR we YN tt 1 Y 7 we A fe Mwy No t UR d ba Figure 3 5 Experimental and calculated 3 P MAS NMR spectra of a powder sample of a phosphinidene ruthenium cluster 54 January 6 2009 Chapter 3 Spin Systems Compounds A 31P Single Crystal and CP MAS NMR Study J Am Chem Soc 1995 117 6961 6969 55 January 6 2009 Chapter 3 Spin Syst
79. monuclear pair of magnetically equivalent spin 1 2 nuclei or a heteronuclear pair A2 or AX approximation It is assumed that the dipolar interaction and the anisotropy are both collinear and axially symmetric Purpose Rel Intensity p 70 Tie to previous site p 70 Convention p 70 Delta 11 Delta 22 Delta 33 p 70 Delta iso Span Skew p 70 Delta iso Anisotropy Asymmetry p 70 Coupled to p 73 N A p 73 D p 73 J p 73 Delta J p 74 Alpha p 74 Beta p 74 LB p 28 Relative intensity of this site in percent Ties parameters to those of the previous site Convention used for chemical shift tensor compo nents Principal components of chemical shift tensor stan dard convention in ppm Principal components of chemical shift tensor Herzfeld Berger convention Principal components of chemical shift tensor Hae berlen convention Specifies the nucleus the observed nucleus is cou pled to If this is the same isotope as the ob served nucleus the checkbox homonuclear be comes checked Natural abundance in percent of the coupled nu cleus If smaller than 100 WSolids1 automatically includes calculation of the spectrum of the uncou pled spin species Direct dipole dipole coupling constant in Hz Indirect spin spin coupling constant in Hz Anisotropy of the indirect spin spin coupling in Hz Azimuth angle in degrees of the internuclear vec tor in the principal a
80. n this file acq this is a text file describing the acquisition parameters used in acquiring the data file These parameters can also be used for a prescription on how to acquire NMR data The meaning of the acquisition parameters depends on the definitions used in the associated pulse program WSolids1 is mainly interested in SF and SW proc this is a text file containing parameters which describe the current state of the data file and the previous operations that have been performed on the data since it was acquired WSolids1 is mainly interested in datatype domain1 current_sizel rmp1 rmv1 rmvunits1 SOLIDS This type of file format is produced by Solids the FORTRAN predecessor of WSolids1 and was created to allow a slightly more general interface in terms of file formats ASCII files created by WIN NMR require only minor editing of the file header in order to conform to this format the text and some lines need to be deleted In order to be recognized by WSolids1 as SOLIDS file the ASCII data file need to adhere to the fol lowing format where each parameter is on a separate row number of points SI spectrometer frequency in MHz SF digital resolution in Hz per point F1 F2 SD highest frequency i e frequency of first point in Hz F1 lowest frequency i e frequency of last point in Hz F2 intensity data as integers or floating point numbers each in a separate row JCAMP DX The JCAMP DX Joint Commit
81. nation with SI p 26 these parameters determine the digital resolution 26 January 6 2009 Chapter 2 Menus Use Relative Threshold Value In the Spectrum Default Parameter p 25 box the status of the checkbox for using relative threshold values determines the time required to do a convolution Checkbox Meaning status mj The mixed Gaussian Lorentzian line shape used in the convolu tion process is used until the intensity of the wings reaches zero This is the more lengthy process but may be required if weak peaks are to be displayed in the presence of very strong peaks Y The mixed Gaussian Lorentzian line shape used in the convo lution process is used until the intensity of the wings reaches 1 10000 of the greatest spectral intensity This reduces calcula tion time but may produce funny looking line shapes for weak peaks Site Dependent Broadening In the Spectrum Default Parameter p 25 box the status of the checkbox for site dependent broad ening determines whether each site requires its own set of convolution parameters p 28 Because the Gaussian Lorentzian peaks used for convolution are normalized the relative areas of each site are approximately preserved Checkbox Meaning status E Usually the selection of no site dependent broadening will do In this case only one set of convolution parameters will be nec essary The convolution routine is activated only once after all site specific spe
82. nd the results have been published in K Eichele G Ossenkamp R E Wasylishen T S Cameron J F Britten Phosphorus 31 Solid State NMR Studies of Homonuclear Spin Pairs in Molybdenum Phosphine Com plexes Single Crystal Dipolar Chemical Shift Rotational Resonance and 2D Spin Echo NMR Experi ments Inorg Chem 1999 38 639 651 49 January 6 2009 Chapter 3 Spin Systems 3 4 Static Quadrupolar Nucleus Static Quadrupolar Nucleus CSA Coupling 2nd order Site 4 Rel Intensity 100 000 _ Tie to previous site 0 120 0 000 viCT viST Convention 0 000 0 000 0 000 0 000 0 000 0 000 Delta 11 Delta 22 Delta 33 Alpha Beta Gamma eronucleus Parameter STANDARD Coupled to N Spin 3 2 B 11 Y 100 000 D deg J Alpha Beta deg deg 3500 000 0 000 0 000 0 000 Calculates the static powder spectrum of a quadrupolar nucleus considering the quadrupolar inter action up to second order Additionally chemical shift anisotropy dipolar and indirect coupling to a heteronucleus can be added note quadrupolar interaction if any is neglected for the coupled het Purpose Rel Intensity p 70 Tie to previous site p 70 Convention p 70 Delta 11 Delta 22 Delta 33 p 70 Delta iso Span Skew p 70 Delta iso Anisotropy Asymmetry p 70 Alpha Beta Gamma p 75 Chi p 79 Eta p
83. ns main window e CTRL F6 or CTRL TAB switches among document windows in the MDI application s workspace ALT TAB switches among applications on the Windows desktop e ALT HYPHEN invokes the system menu of the active document window ALT SPACEBAR invokes the system menu of the active application s main window 13 January 6 2009 Chapter 1 Getting Started 1 5 Keyboard Accelerators ALT F4 ALT HYPHEN ALT SPACEBAR ALT TAB CTRL F4 CTRL F6 CTRL TAB ENTER C E N closes an application s main window invokes the system menu of the active document window invokes the system menu of the active application s main window switches among applications on the Windows desktop closes the currently active document window switches among document windows in the MDI application s workspace switches among document windows in the MDI application s workspace perform the next step of the cycle feature Calculate Edit sites New Site 14 January 6 2009 2 Menus Contents 21 Pe Menu ciii ini aibit koe Ge ke ae ae ade ae a a ee ee 18 211 New Widow 2 bb db ga eb Yb er en ehe 18 Pile TIPE ORCI ot ey hE Se E E a ae ee Bar ans 18 Bruker Topspin KWHNMER c 2 2 2a e ee en 19 Bruker WINNMR Generic 2 0 00 et ee ee 20 Bruker WINNMR UNIX 0000 ee ee ee 20 Bruker WINNMR ASCI occiso e Bs ae we 20 Chemagneties Spimbight o ce caora 2228 we eR REESE eh as 21 SOLIDS ecs Ge Ge e
84. nvestigation of the 31P 31P Spin Spin Coupling Tensor J Phys Chem 1995 99 1030 1037 46 January 6 2009 Chapter 3 Spin Systems Dipolar Chemical Shift A2 AX En r sanoo J Z 2 3 Figure 3 2 Experimental and calculated 3P NMR spectra of a static powder sample of tetraethyl diphosphine disulfide 47 January 6 2009 Chapter 3 Spin Systems 3 3 Static Dipolar Chemical Shift AB Homonuclear Two Spin System AB Site 3 730 000 Rel Intensity LUAU E 0 000 _ Tie to previous site Delta J 0 000 Alpha 0 000 Convention STANDARD 52 lt Beta 0 000 Nucleus A Nucleus B Delta 11 269 000 Delta 11 269 000 Delta 22 114 000 Delta 22 114 000 Delta 33 39 00 Delta33 39 0 Alpha 0 000 deg Alpha 0 000 Beta 90 000 deg Beta 90 000 Gamma 25 000 deg Gamma 25 000 Calculates the spectrum of a static powder sample containing an isolated spin pair of homonuclear spin 1 2 nuclei considering chemical shift anisotropy direct dipole dipole coupling and indirect spin spin coupling including second order effects It is assumed that the dipolar and indirect coupling tensors are colinear and axially symmetric Parameter Purpose Rel Intensity p 70 Relative intensity of this site in percent Tie to previous site p 70 Ties parameters to those of the previous site Convention p 70 Convention used for chemical
85. ompound Oef ppm ref 05 1 Cret e Because 0yef is often a small number compared to 1 frequently the following approximation is used Shifts commonly used in solution and solid state NMR studies are thus positive to high frequency Absolute shieldings are positive to low frequency and are only accessible via theoretical calculations The establishment of a correspondence between a chemical shift scale and a chemical shielding scale is not a trivial task and requires both careful theoretical calculations and experimental measurements 2 The nuclear magnetic shielding absolute shielding is the molecular electronic property The chemical shift is a quantity that we experimentalists have defined and use because of our inability to directly measure the absolute magnetic shielding This inability results from our inability to know the magni tude of the magnetic field to an accuracy on the order of parts per billion independent of the resonance exp eriment 3 72 January 6 2009 Chapter 3 Spin Systems Comments The symbol o should only be used for absolute shieldings Often however authors use a pseudo shielding scale where the shielding is obtained by simply reversing the sign of the chemical shift In our opinion this adds only to the confusion without providing any additional insight Note that the exact formulation of the span p 70 Q contains the factor 1 dref 3 O 611 933 1
86. p AQS and eeeppp FQS need to be present in the same directory they are ASCII parameter files of variable record length and start with JCAMP DX format the AQS file contains the parameters SFO1 SW_h O1 and FOS contains OFFSET Bruker WINNMR ASCII WinNMR is able to export spectra in ASCII format depending on the version of WinNMR slight differences arise The file starts with some parameters one on each line and is then followed by pure intensity data each point on its own line Here is the beginning of such a file Data file D NMR ASP3000 KOPOPH3 101001 TXT Starting Point 0 Ending Point 4095 Point Count 4096 Real Data SFO1 81 018000 MHz SF 81 023633 MHz Offset 444 735199 ppm Decim 0 Dspfvs 0 20 January 6 2009 Chapter 2 Menus FW 100000 000000 Hz Sweep Width 83333 333332 Hz Hz Pt 20 345052 First Point 36034 061368 Hz Last Point 47299 271964 Hz First Point 444 735199 PPM Last Point 583 771308 PPM AQmod 2 5759 1961 Chemagnetics SpinSight The Spinsight data format consists of several component files all contained within one directory In order to be recognized by WSolids as SpinSight file the data files need to adhere to the following format data this is a binary file which contains the actual NMR data The storage order is all real values followed by all imaginary values i e the data are unshuffled No formating end of row or end of file characters are present i
87. pin 1 2 Spin S Diag p 58 added handling of general spin 5 2 case any chi any eta any orientation and made some modifications to the spin 3 2 part also 1 3 2 Version 1 17 30 23 05 2001 e Included new Herzfeld Berger tables that are more accurate at higher values of u The tables were calculated using a home made dedicated program on a Pentium 400 MHz PC and required almost a week of computer time 1 3 3 Version 1 17 28 27 09 2000 e Changed the use of the Relative intensity p 70 parameter it is now introduced after the calcu lation for that specific site has been carried out sites using different calculational models should now have relative areas corresponding to their relative intensities This also fixed bugs for some of the models where the relative intensity was not handled properly e Modified the model Static Quadrupolar Nucleus p 50 to allow a homonuclear A2 spin system it is up to the user to decide if the result makes sense A division by zero for not initialized spectrometer frequency gets caught now e Modified the POWDER routine by Alderman previously the interpolation did not cover the half sphere completely 1 3 4 Version 1 17 22 17 03 1999 e Fixed a bug related to the relative intensities of several sites when using the model MAS Quadrupo lar nucleus p 56 e Made changes to the POWDER subroutine to deal with single line lineshapes better previously no intensity got added 1 3 5 Vers
88. relative orientations of chemical shift and dipolar interaction For more general cases the set of three Euler angles is required 3 12 14 Euler Angles The triplet of Euler angles a p y is useful to describe rotations or relative orientations of orthogonal coordinate systems Unfortunately their definition is not unique and in the literature there are as many different conventions as authors The convention employed here is one of the more common ones All rotations are in a counter clockwise fashion right handed mathematically positive sense The Euler angles a f y relate two orthogonal coordinate systems having a common origin The transition from one coordinate system to the other is achieved by a series of two dimensional rotations The rotations are performed about coordinate system axes generated by the previous rotation step the step by step procedure is illustrated in the topic Rotation Matrices p 75 and a more humorous account is given in topic The Swivel Chair p 78 The convention used here is that is a rotation about the Z axis of the initial coordinate system About the y axis of this newly generated coordinate system a rotation by is performed followed by a rotation by about the new z axis Given the Euler angles the step by step procedure illustrates how to move from one coordinate system to the other However given the two coordinate systems how can one determine the Euler angles relating them This
89. s Window Help Alsr szamomz ioli Static Quadrupolar Nucleus CSA Coupling 2nd order Site 1 i 0 148 Rel Intensity ANI Eta 0 980 _ Re to previeus site v CT v ST Convention STANDARD Coupled to C 13 hd Delta 11 f N A Delta 22 Spin 1 2 Delta 33 Alpha Beta Gamma Figure 3 4 Experimental and calculated 13Cs NMR spectra of a static powder sample of cesium cad mium thiocyanate Beta p 74 Polar angle in degrees of the internuclear vector in the principal axis system of the electric field gradi ent tensor LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Background In addition to the chemical shift anisotropy CSA the spectrum of a quadrupolar nucleus will also depend on the nuclear quadrupolar interaction and the relative orientation of both interactions The quadrupolar interaction is considered up to second order for the observed nucleus Optionally dipo lar and indirect coupling to a heteronucleus can be added note quadrupolar interaction if any is neglected for the coupled heteronucleus 3 4 1 Implementation Details Specifically we use the following conventions e the NQR notation is used for labelling the axes of the EFG tensor VZZ gt VYY gt VXX e the orientation of the field is given by
90. shift tensor compo nents Delta 11 Delta 22 Delta Principal components of chemical shift tensor stan 33 p 70 dard convention in ppm Delta iso Span Skew p Principal components of chemical shift tensor 70 Herzfeld Berger convention Delta iso Anisotropy Principal components of chemical shift tensor Hae Asymmetry p 70 berlen convention Alpha Beta Gamma p Euler angles in degrees for going from the crystal 75 frame to the principal axis system of the chemical shift tensors D p 73 Direct dipole dipole coupling constant in Hz J 73 Indirect spin spin coupling constant in Hz Delta J p 74 Anisotropy of the indirect spin spin coupling in Hz Alpha p 74 Azimuth angle in degrees of the internuclear vec tor in the principal axis system of the chemical shift tensor Beta p 74 Polar angle in degrees of the internuclear vector in the principal axis system of the chemical shift tensor LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box 48 January 6 2009 Chapter 3 Spin Systems File Simulation Tools Window Help T 10 Homonuclear Two Spin System AB x Lx A Site 1 D 690 000 Hz Rel Intensity J 145 000 Hz _ Re to previous site Delta J 0 000 Hz Alpha 0 000 de Convention Hae
91. sign There is no quick fix right now contact me if you need more information 42 January 6 2009 3 Spin Systems 3 1 Static Chemical Shift Anisotropy Chemical Shift Anisotropy Site 1 Rel Intensity AUU L Be te previous site Convention STANDARD F Delta 11 100 000 ppm Delta 22 50 000 ppm Delta 33 100 000 ppm This model calculates the spectrum of a static powder sample showing only chemical shift anisotropy powder pattern Parameter Purpose Rel Intensity p 70 Relative intensity of this site in percent Tie to previous site p 70 Ties parameters to those of the previous site Convention p 70 Convention used for chemical shift tensor compo nents Delta 11 Delta 22 Delta Principal components of chemical shift tensor stan 33 p 70 dard convention in ppm Delta iso Span Skew p Principal components of chemical shift tensor 70 Herzfeld Berger convention Delta iso Anisotropy Principal components of chemical shift tensor Hae Asymmetry p 70 berlen convention LB p 28 Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box Background Depending on the local symmetry at the nuclear site the magnitude of the chemical shift will vary as a function of the orientation of the molecule with respect to the external magnetic field
92. spin system 30 31 spinning 67 SpinSight 21 standard 57 tie 57 tools 34 TopSpin 19 trademarks 69 trouble 6 Varian 22 VAS 55 56 warranty 70 window 37 WinNMR 20 22 XWINNMR 20 XWinNMR 19 86 January 6 2009
93. tation in WSolids1 Managing multiple documents is one of the key issues 1 4 1 The Multiple Document Interface The multiple document interface MDI has been designed for applications that need to simultaneously manage e more than one data set e more than one view of a data set In MDI there are two fundamentally different type of windows e The main window of an MDI application is called a frame window Frame windows usually have a title bar a menu a system menu a sizing border Minimize Maximize buttons The non client area of the frame window surrounds a portion of something called the application workspace The workspace can be larger than the frame window s client area because a user can use scroll bars to scroll different portions of the workspace into view e An MDI application s workspace can contain zero or more child windows which are referred to as documents document windows or MDI children In the case of WSolids1 a document window usually corresponds to a window with dual display of an experimental and a calculated spectrum We shall call such a document window a spectrum window In general document windows have a title bar a sizing border a system menu bitmap Minimize Maximize buttons scroll bars Because document windows always have Minimize and Maximize buttons they can be minimized and maximized When minimized they are represented as icons and displayed
94. tee on Atomic and Molecular Physical Data Exchange format has been initiated by IUPAC to achive better long term archival and exchange of spectroscopic data The main features 1 are first non binary approach ever 21 January 6 2009 Chapter 2 Menus e vendor independent JCAMP is not owned by anybody e printable characters only important for e mail etc e reasonable compression rates long before LHARC etc did show up e extendable and open definitions to allow further improvements In my opinion this was a good idea in principle However in practice the standard is too unclear in several aspects thus writing an import filter for such data is a royal pain WSolids1 checks for the following parameters TITLE JCAMP DX with values of 4 24 5 00 or 5 01 DATA TYPE NPOINTS OBSERVE FREQUENCY FIRSTX LASTX XFACTOR DATA CLASS Currently only XY DATA are supported References 1 posting by Dr Michael Grzonka in the newsgroup bionet structural nmr Subject The JCAMP standard of spectroscopic data transfer a summary on 29 January 1996 2 McDonald Wilks Appl Spectrosc 1988 42 151 3 Davies Lampen Appl Spectrosc 1993 47 1093 4 Lampen Lambert Lancashire McDonald McIntyre Rutledge Fr hlich Davies Pure Appl Chem 1999 71 1549 Simpson SIMPSON A General Simulation Program for Solid State NMR Spectroscopy was the title of the paper 1 that introduced SIMPSON Its output is an
95. the polar angle beta wrt VZZ and the azimuth alpha the angle between the projection of B into the VXX VYY plane and VXX cf Abragam e direction cosines of the shielding tensor with respect to the EFG frame are obtained via the Euler angles following Arfken s convention with the initial alignment 11 XX 22 YY 33 ZZ Figure 3 4 shows an example for the succesful simulation of a spectrum of a quadrupolar nucleus that shows the combined effect of chemical shift anisotropy and quadrupolar interaction in a powder sample It is the 133Cs NMR spectrum of cesium cadmium thiocyanate CsCd SCN 3 and the results 51 January 6 2009 Chapter 3 Spin Systems have been published in S Kroeker K Eichele R E Wasylishen J F Britten Cesium 133 NMR Study of CsCd SCN 3 Relative Orientation of the Chemical Shift and Electric Field Gradient Tensors J Phys Chem B 1997 101 3727 3733 3 4 2 References 1 The first order expression is taken from Amoureux s treatment which follows Abragam and Taulelle Amoureux Fernandez Granger In Multinuclear Magnetic Resonance in Liquids and Solids Chemi cal Applications Granger Harris eds Kluwer Academic Publishers 1990 Ch 22 p 409 2 The second order expression is taken from G H Stauss J Chem Phys 1964 40 1988 3 Related papers K Narita J I Umeda H Kusumoto J Chem Phys 1966 44 2719 J F Baugher P C Taylor T Oja P J Bray J Chem Phys 1969
96. ties of merchantability and fitness for a particular purpose the entire risk as to the quality and performance of the contents of this package is with you should this package prove defective you assume the cost of all necessary servicing repair or correction in no event unless required by applicable law or agreed to in writ ing will any copyright holder or any other party who may modify and or redistribute this package as permitted in the license be liable to you for damages including any general special incidental or consequential damages arising out of the use or inability to use the package including but not 82 January 6 2009 Chapter 4 Acknowledgements limited to loss of data or data being rendered inaccurate or losses sustained by you or third parties even if such holder or other party has been advised of the possibility of such damages In any case liability will be limited to the amount of money that the copyright holder received from you for the use of this program 83 January 6 2009 Chapter 4 Acknowledgements 84 January 6 2009 Index A2 55 AB 56 absolute shielding 59 absolute value 36 absorption 29 abundance 60 accelerators 14 acknowledgements 69 alpha 61 anisotropy in indirect coupling 61 apodization 27 28 AX 55 beginner 5 beta 61 Bruker 19 20 bugs 39 calculation 24 32 central transition 67 changes 10 Chemagnetics 21 chemical shift 59 chemical shift
97. um window Multiply Scale up the intensities of spectra in the currently active spectrum window Divide Scale down the intensities of spectra in the currently active spectrum window Reset display Resets the display limits such that the spectra are fully visible Cascade Cascade all open spectrum windows Tile Arrange all open spectrum windows so that each has the same area Arrange Icons Arrange the icons of minimized spectrum windows Close All Close all spectrum windows 40 January 6 2009 Chapter 2 Menus 2 5 Help Menu The Help menu allows access to a variety of information It consists of the following items WSolids1 File Simulation Tools Window Es Index F1 Search for About Item Action Index Open the WSolids1 help file on its table of contents page Search for Call the WSolids1 help file and search for a specific keyword in a list of predefined keywords Note that the help file also provides a full text search feature activated with the Search button About Displays information about the current version and build number of WSolids1 41 January 6 2009 Chapter 2 Menus 2 6 Known Problems Usually I will try to keep the content of this page as small as possible e There is a problem in the MAS Spin 1 2 Spin S Diag p 58 model when the observed nucleus has a negative magnetogyric ratio In these cases it might appear that the quadrupolar coupling constant has the opposite
98. xis system of the chemical shift tensor Polar angle in degrees of the internuclear vector in the principal axis system of the chemical shift tensor Provides access to the convolution parameters for the current site To have individual convolution pa rameters for each site specify this in the Spectrum Default Parameters p 25 box 45 January 6 2009 Chapter 3 Spin Systems Background In addition to the chemical shift anisotropy CSA the spectrum of a spin pair will also depend on the direct dipolar coupling and potentially the indirect spin spin coupling between both nuclei Because both the CSA and dipolar interaction are tensorial interactions the actual line shape also depends on their relative orientation For historical reasons this model works slightly different from the other models Via the parameters relative intensity and natural abundance one can calculate coupled and uncoupled spectra directly without defining a separate spin system for each This is ok for spin systems where the observed nucleus is coupled to an NMR active isotope and an NMR passive isotope However to deal with situations where the observed nucleus is coupled to an NMR passive isotope and several different NMR active isotopes the generation of several spin systems is required Example P 31 coupled to cadmium Cd 111 12 75 Cd 113 12 26 passive 74 99 One could use three different sites with the relative intensity reflecting the
99. y out of this software that I develop and maintain in the evening hours 1 1 3 License This program package can be used without any fee However if you find this program useful and publish results obtained by using WSolids1 we would appreciate a citation or acknowledgement of this program similar to WSolids1 K Eichele R E Wasylishen Dalhousie University Halifax Canada Before reading on you may also want to have a look at our credits statement p 81 trademark acknowledgement p 82 copyright message p 82 and obligatory disclaimer p 82 7 January 6 2009 Chapter 1 Getting Started 1 1 4 Trouble Although WSolids1 has been tested and used both in house and by others it is always possible that errors exist Some errors may become apparent after detailed use on the wide variety of chemical systems It is the responsibility of the user to determine the correctness of the results If errors are noticed please notify us of your problems and the prescribed or suggested corrections so that others may benefit from the improved code Also suggestions for improvements are welcome Inquiries about the use of this program or reports of problems can be directed via e mail to Klaus Eichele uni tuebingen de Also you may address correspondence via snail mail to Dr Klaus Eichele Institut fuer Anorganische Chemie Universitaet Tuebingen Auf der Morgenstelle 18 D 72076 Tuebingen Germany 8 January 6 2009

WSolids1 User Manual - Pascal-Man

Contents

Download Pdf Manuals

Related Search

Related Contents