Nonempirical calculations of the one-bond (29)Si-(13)C spin-spin coupling constants taking into account relativistic and solvent corrections

The computational study of the one-bond (29)Si-(13)C spin-spin coupling constants has been performed at the second-order polarization propagator approximation (SOPPA) level in the series of 60 diverse silanes with a special focus on the main factors affecting the accuracy of the calculation includin...

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Bibliographic Details
Published in:Magnetic resonance in chemistry Vol. 52; no. 8; p. 413
Main Authors: Rusakova, Irina L, Rusakov, Yury Yu, Krivdin, Leonid B
Format: Journal Article
Language:English
Published: England 01.08.2014
Subjects:
relativistic corrections
DFT-PBE0
SOPPA(CCSD)
basis set
solvent effects
SOPPA
SOPPA(CC2)
29Si NMR
silanes
29Si-13C spin-spin coupling constant
ISSN:1097-458X, 1097-458X
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Summary:The computational study of the one-bond (29)Si-(13)C spin-spin coupling constants has been performed at the second-order polarization propagator approximation (SOPPA) level in the series of 60 diverse silanes with a special focus on the main factors affecting the accuracy of the calculation including the level of theory, the quality of the basis set, and the contribution of solvent and relativistic effects. Among three SOPPA-based methods, SOPPA(MP2), SOPPA(CC2), and SOPPA(CCSD), the best result was achieved with SOPPA(CCSD) when used in combination with Sauer's basis set aug-cc-pVTZ-J characterized by the mean absolute error of calculated coupling constants against the experiment of ca 2 Hz in the range of ca 200 Hz. The SOPPA(CCSD)/aug-cc-pVTZ-J method is recommended as the most accurate and effective computational scheme for the calculation of (1)J(Si,C). The slightly less accurate but essentially more economical SOPPA(MP2)/aug-cc-pVTZ-J and/or SOPPA(CC2)/aug-cc-pVTZ-J methods are recommended for larger molecular systems. It was shown that solvent and relativistic corrections do not play a major role in the computation of the total values of (1)J(Si,C); however, taking them into account noticeably improves agreement with the experiment. The rovibrational corrections are estimated to be of about 1 Hz or 1-1.5% of the total value of (1)J(Si,C).
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ISSN:1097-458X
1097-458X
DOI:10.1002/mrc.4080