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One-bond 29Si-1H spin-spin coupling constants in the series of halosilanes: benchmark SOPPA and DFT calculations, relativistic effects, and vibrational corrections


Correspondence to: Leonid B. Krivdin, A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033 Irkutsk, Russia. E-mail:


A number of most representative second order polarization propagator approach (SOPPA) based wavefunction methods, SOPPA, SOPPA(CC2) and SOPPA(CCSD), and density functional theory (DFT) based methods, B3LYP, PBE0, KT2, and KT3, have been benchmarked in the calculation of the one-bond 29Si-1H spin-spin coupling constants in the series of halosilanes SiHnX4−n (X = F, Cl, Br, I), both at the non-relativistic and full four-parameter Dirac's relativistic levels taking into account vibrational corrections. At the non-relativistic level, the wavefunction methods showed much better results as compared with those of DFT. At the DFT level, out of four tested functionals, the Perdew, Burke, and Ernzerhof's PBE0 showed best performance. Taking into account, relativistic effects and vibrational corrections noticeably improves wavefunction methods results, but generally worsens DFT results. Copyright © 2013 John Wiley & Sons, Ltd.