Rusakov Yury Yu, Krivdin Leonid B
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, Favorsky St. 1, 664033 Irkutsk, Russia.
Magn Reson Chem. 2013 Sep;51(9):557-61. doi: 10.1002/mrc.3986. Epub 2013 Jul 8.
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 (29)Si-(1)H spin-spin coupling constants in the series of halosilanes SiH(n)X(4-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.
在考虑振动校正的情况下，已在非相对论和全四参数狄拉克相对论水平上，对一系列卤硅烷SiH(n)X(4-n)（X = F、Cl、Br、I）中一键(29)Si-(1)H自旋-自旋耦合常数的计算进行了基准测试，这些方法包括一些最具代表性的基于二阶极化传播子方法（SOPPA）的波函数方法，即SOPPA、SOPPA(CC2)和SOPPA(CCSD)，以及基于密度泛函理论（DFT）的方法，即B3LYP、PBE0、KT2和KT3。在非相对论水平上，与DFT方法相比，波函数方法显示出更好的结果。在DFT水平上，在四种测试泛函中，佩德韦、伯克和恩泽尔霍夫的PBE0表现最佳。考虑相对论效应和振动校正会显著改善波函数方法的结果，但通常会使DFT结果变差。
