Benchmark calculations of (29) Si-(1) H spin-spin coupling constants across double bond

Yury Yu Rusakov; Leonid B Krivdin; Valentina M Nosova; Alexander V Kisin

doi:10.1002/mrc.2878

Benchmark calculations of (29) Si-(1) H spin-spin coupling constants across double bond

Magn Reson Chem. 2012 Apr;50(4):278-83. doi: 10.1002/mrc.2878. Epub 2012 Mar 13.

Authors

Yury Yu Rusakov¹, Leonid B Krivdin, Valentina M Nosova, Alexander V Kisin

Affiliation

¹ A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033, Irkutsk, Russia.

PMID: 22416027
DOI: 10.1002/mrc.2878

Abstract

Benchmark calculations of geminal and vicinal (29) Si-(1) H spin-spin coupling constants across double bond in three reference alkenylsilanes have been carried out at both DFT and SOPPA levels in comparison with experiment. At the former, four density functionals, B3LYP, B3PW91, PBE0 and KT3, were tested in combination with five representative basis sets. At the latter, three main SOPPA-based methods, SOPPA, SOPPA(CC2) and SOPPA(CCSD), were examined in combination with the same series of basis sets. On the whole, the wavefunction methods showed much better results as compared to DFT, with the most efficient combination of SOPPA/cc-pVTZ-su2 characterized by a mean absolute error of only 0.4 Hz calculated for a set of nine coupling constants in three compounds with a sample span of around 40 Hz.