Autschbach Jochen
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, USA.
J Chem Phys. 2007 Sep 28;127(12):124106. doi: 10.1063/1.2768363.
An analysis method for static linear response properties employing two-component (spin-orbit) relativistic density functional theory along with scalar relativistic "natural localized molecular orbitals" (NLMOs) and "natural bond orbitals" (NBOs) has been developed. The spin-orbit NLMO/NBO analysis has been applied to study the indirect spin-spin coupling (J-coupling) constants in Tl-I, PbH(4), and a dinuclear Pt-Tl bonded complex with a very large Pt-Tl coupling constant (expt.: 146.8 kHz). For Tl-I it is shown that the analysis scheme based on scalar relativistic NLMOs is applicable even if spin-orbit coupling is responsible for most of the coupling's magnitude. For PbH(4) it is shown that electron delocalization plays a much larger role for the Pb-H coupling than it is the case for the C-H coupling in methane. For the Pt-Tl complex the analysis clearly demonstrates the strong influence of the ligands on the Pt-Tl coupling constant and quantifies the effect of the delocalization of the Pt-Tl bond on the Pt-Tl coupling constant.
一种采用双组分（自旋-轨道）相对论密度泛函理论以及标量相对论“自然定域分子轨道”（NLMOs）和“自然键轨道”（NBOs）的静态线性响应性质分析方法已被开发出来。自旋-轨道NLMO/NBO分析已被应用于研究Tl-I、PbH₄以及具有非常大的Pt-Tl耦合常数（实验值：146.8 kHz）的双核Pt-Tl键合配合物中的间接自旋-自旋耦合（J-耦合）常数。对于Tl-I，结果表明基于标量相对论NLMOs的分析方案即使在自旋-轨道耦合对大部分耦合量起作用时也是适用的。对于PbH₄，结果表明电子离域对Pb-H耦合的作用比对甲烷中C-H耦合的作用大得多。对于Pt-Tl配合物，该分析清楚地证明了配体对Pt-Tl耦合常数的强烈影响，并量化了Pt-Tl键的离域对Pt-Tl耦合常数的影响。
