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Benchmark calculations of 29 Si– 1 H spin–spin coupling constants across double bond
Author(s) -
Rusakov Yury Yu.,
Krivdin Leonid B.,
Nosova Valentina M.,
Kisin Alexander V.
Publication year - 2012
Publication title -
magnetic resonance in chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.483
H-Index - 72
eISSN - 1097-458X
pISSN - 0749-1581
DOI - 10.1002/mrc.2878
Subject(s) - chemistry , coupling constant , spin (aerodynamics) , double bond , coupling (piping) , atomic physics , computational chemistry , analytical chemistry (journal) , physics , thermodynamics , organic chemistry , mechanical engineering , particle physics , engineering
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. Copyright © 2012 John Wiley & Sons, Ltd.