Re: CCL:Paramagnetically shifted 1H NMR spectra
- From: Arvydas Tamulis <tamulis $#at#$ itpa.lt>
- Subject: Re: CCL:Paramagnetically shifted 1H NMR spectra
- Date: Tue, 13 Feb 2001 09:12:56 +0200 (EET)
Dear Dauoglas Fox and other Netters who responded me during last days
concerning calculations of paramagnetically shifted 1H NMR spectra
possessing up to 135 ppm values.
During last days I clearified that for large (100 ppm) paramagnetic
1H shifts are responsible not good basis sets (only few ppm) and not
electron correlations (only tens ppm) but including relativistic effects:
'electron spin-orbit', 'electron spin-spin', and 'electron spin - proton
spin', etc. couplings. I do not know what relativism it is included in DALTON
and DIRAC packages (maybe here can respond experts from these teams) but
for my opinion if it is included 'electron spin - proton spin' coupling
that should give these 100 ppm paramagnetic shifts in 1H NMR spectra.
Maybe in other programs people are doing such a inclusions of
'electron spin - proton spin couplings'?
I would be appreciate if somebody will allow me to perform trial calculations
of biliverdin CuOEB molecule 1H NMR spectrum using DALTON, DIRAC or other
program with implemented as much as possible relativistic effects.
Thanking your in advance for further discussions and advises.
Yours sincerely, Arvydas Tamulis
Enclosed please find X-Ray geometry of CuOEB molecule in Angstroms:
Cu1 0. 0. 0.
O2 0.2239 -2.96653 -1.55039
N3 1.38133 -1.33544 -0.35323
N4 1.38119 1.34207 0.36885
C5 1.22628 -2.58553 -0.97483
C6 2.51385 -3.33756 -0.86868
C7 3.37827 -2.55016 -0.22896
C8 2.67395 -1.28282 0.09472
C9 3.26426 -0.17877 0.65202
C10 2.68854 1.08761 0.70813
C11 3.38244 2.34651 0.96318
C12 2.50269 3.34699 0.72477
C13 1.25013 2.71593 0.35196
C14 0.0751 3.37078 0.
C15 2.68652 -4.68205 -1.49633
C16 3.05674 -4.56912 -2.96369
C17 4.84657 -2.77602 0.04178
C18 5.72923 -2.08939 -1.00856
C19 4.85471 2.43112 1.27447
C20 5.69449 2.34802 0.0041
C21 2.72592 4.83225 0.72854
C22 2.87181 5.41601 -0.67222
H23 4.13917 -0.29105 1.00274
H24 0.09707 4.35684 0.
H25 1.8737 -5.18468 -1.40342
H26 3.37402 -5.20107 -1.07412
H27 3.13618 -5.45897 -3.37019
H28 2.36288 -4.06322 -3.3895
H29 3.87718 -4.07992 -3.05734
H30 5.00432 -3.74715 0.00503
H31 5.07799 -2.46117 0.91361
H32 6.64112 -2.28581 -0.82449
H33 5.51113 -2.4159 -1.88189
H34 5.58593 -1.11668 -0.96462
H35 5.10459 1.68705 1.84642
H36 5.03303 3.27735 1.73233
H37 6.61722 2.41078 0.21711
H38 5.52484 1.4978 -0.44582
H39 5.45344 3.10135 -0.56135
H40 3.50226 5.01567 1.24612
H41 1.98737 5.25961 1.1645
H42 3.01354 6.38803 -0.58859
H43 3.62122 5.00544 -1.10604
H44 2.09038 5.25163 -1.1876
N45 -1.43943 -1.27259 0.35323
N46 -1.32005 1.40226 -0.36885
C47 -1.12793 2.76892 -0.35196
C48 -1.34022 -2.52835 0.97483
C49 -2.72843 -1.16245 -0.09472
C50 -2.63743 1.20627 -0.70813
C51 -2.35113 3.45514 -0.72477
O52 -0.3558 -2.95361 1.55039
C54 -2.66 -3.22228 0.86868
C55 -3.4885 -2.39716 0.22896
C56 -3.26899 -0.0332 -0.65201
C57 -3.27458 2.49484 -0.96318
C58 -2.50799 4.94886 -0.72854
C59 -2.89238 -4.55775 1.49633
C60 -4.9654 -2.5574 -0.04178
H61 -4.14802 -0.1064 -1.00274
C62 -4.74161 2.64493 -1.27447
C63 -2.62775 5.53854 0.67222
H64 -3.2754 5.16668 -1.24612
H65 -1.75115 5.34291 -1.1645
C66 -3.2572 -4.42844 2.96368
H67 -2.10276 -5.09608 1.40342
H68 -3.60232 -5.04563 1.07412
C69 -5.8166 -1.83214 1.00856
H70 -5.16625 -3.52054 -0.00503
H71 -5.18257 -2.23255 -0.91362
C72 -5.58426 2.59932 -0.0041
H73 -5.02439 1.91273 -1.84642
H74 -4.88207 3.49828 -1.73233
H75 -2.72604 6.51592 0.58859
H76 -3.3947 5.16177 1.10604
H77 -1.85441 5.33953 1.1876
H78 -3.37619 -5.31387 3.37019
H79 -2.5415 -3.95395 3.3895
H80 -4.05504 -3.90319 3.05734
H81 -6.73633 -1.98774 0.82449
H82 -5.61326 -2.16804 1.88189
H83 -5.63012 -0.86678 0.96462
H84 -6.50328 2.70312 -0.21711
H85 -5.45265 1.74239 0.44582
H86 -5.3099 3.34117 0.56135
***********************************************************
>
On Mon, 12 Feb 2001, Cust. Service Doug wrote:
>
> Dr. Tamulis,
>
> I don't have ready access to this journal at my office. Can
> you send the structure you used? Have you verified that the
> environment around these protons is reasonably described by this
> input structure?
>
> Generally the shifts in proton NMR calculations are good only to
> about 10% which makes them less appropriate for structural studies
> but the wide range you report from the experiment should be reproduced
> at least qualitatively.
>
> >
> > Dear Netters,
> >
> > We did not succeeded to calculate paramagnetically shifted 1H NMR
spectrum
> > of biliverdin molecule CuOEB using Gaussian 98 (see experimental data
in
> > J. Am. Chem.Soc., vol. 115, p. 12206 (1993)).
> >
> > We have optimized geometry of TeMeSilane molecule and obtained from
NMR
> > calculation the Isotropic Shielding values for H atoms (in ppm):
> >
> > H Isotropic = 31.9027 Anisotropy = 9.6413
> > XX= 29.4642 YX= 0.2951 ZX= -0.7329
> > XY= 0.4642 YY= 32.9871 ZY= -5.1492
> > XZ= -0.8947 YZ= -5.1015 ZZ= 33.2567
> > Eigenvalues: 27.9348 29.4430 38.3302
> >
> > We have used Density Functional Theory B3PW91/6-311G**
> >
> > We have taken geometry of CuOEB from X-Ray experiment.
> > Our B3PW91\6-311G** calculated CuOEB NMR Hm shielding values (ppm):
> > 23 H Isotropic = 28.4781 Anisotropy = 10.0683
> > XX= 24.0637 YX= -1.2135 ZX= -.8179
> > XY= -.0906 YY= 35.1141 ZY= -2.2717
> > XZ= 9.0739 YZ= 1.6948 ZZ= 26.2566
> > Eigenvalues: 20.8808 29.3633 35.1904
> >
> > 60 H Isotropic = 27.5216 Anisotropy = 12.3793
> > XX= 22.4061 YX= 2.7621 ZX= -1.0495
> > XY= -.3733 YY= 35.4454 ZY= 2.7019
> > XZ= 10.0293 YZ= -6.4196 ZZ= 24.7134
> > Eigenvalues: 18.6646 28.1258 35.7745
> >
> > and shielding Hm' value:
> > 24 H Isotropic = 25.8868 Anisotropy = 16.3237
> > XX= 36.5750 YX= -.6396 ZX= 4.7813
> > XY= -.0379 YY= 23.9614 ZY= .1694
> > XZ= -.9100 YZ= 2.3766 ZZ= 17.1241
> > Eigenvalues: 16.7005 24.1907 36.7693
> >
> > It means that our calculated chemical shifts for Hm and Hm' are equal
to
> > few ppm while CuOEB experimental NMR chemical shift values for Hm and
Hm' in
> > J. Am. Chem.Soc., vol 115, p. 12206 are equal approximately to 135 ppm
and
> > -100 ppm.
> >
> > Why so badly we have calculated paramagnetically shifted 1H NMR
spectrum
> > for CuOEB molecule?
> > Maybe GAUSSIAN is not able to calculate paramagnetically shifted 1H
NMR
> > spectra?
> > Which program is suitable for calculations of paramagnetically shifted
1H
> > NMR spectra?
> >
> > Thanking your in advance.
> > With best regards, Arvydas Tamulis & Jelena Tamuliene
> > *******************************************************
> > Arvydas Tamulis
> >
> > Doctor of Natural Sciences, senior research fellow
> >
> > Institute of Theoretical Physics and Astronomy,
> > Theoretical Molecular Electronics Research Group,
> > A. Gostauto 12, Vilnius 2600, Lithuania
> > e-mail: TAMULIS $#at#$ ITPA.lt; WEBsite: http://www.itpa.lt/~tamulis/
> > fax: +(370-2)-225361 or +(370-2)-224694
> > Phone: +(370-2)-620861
> > Home address: Didlaukio 27-40, Vilnius 2057, Lithuania
> > Phone: +(370-2)-778743
> >
> >
> >
> >
> >
> >
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> --
>
> Douglas J. Fox
> Technical Support
> Gaussian, Inc.
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