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首页> 外文期刊>The Journal of Chemical Physics >Model core potentials for studies of scalar-relativistic effects and spin-orbit coupling at Douglas-Kroll level. I. Theory and applicationsto Pb and Bi
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Model core potentials for studies of scalar-relativistic effects and spin-orbit coupling at Douglas-Kroll level. I. Theory and applicationsto Pb and Bi

机译：模型核心潜力，用于研究道格拉斯·克罗尔（Douglas-Kroll）级的标量相对论效应和自旋轨道耦合。一，Pb和Bi的理论与应用

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摘要

A theory of model core potentials that can treat spin-orbit-coupling (SOC) effects at the level ofDouglas–Kroll formalism has been developed. By storing the damping effect of kinematic operatorin the Douglas–Kroll spin-orbit operator into an additional set of basis set contraction coefficients,the Breit–Pauli spin-orbit code in the GAMESS-US program was successfully used to performDouglas–Kroll spin-orbit calculations. It was found that minute errors in the radial functions ofvalence orbitals lead to large errors in the spin-orbit energy levels and thus fitting the radial part ofthe spin-orbit matrix elements is necessary in model core potential parametrization. The first modelcore potentials that include the new formalism were developed for two 6p-block elements, Pb andBi. The valence space of the 5p, 5d, 6s, and 6p orbitals was used because of the large SOC betweenthe 5p and 6p orbitals. The model core potentials were validated in the calculations of atomicproperties as well as spectroscopic constants of diatomic metal hydrides. The agreement betweenresults of the model core potential and all-electron calculations was excellent, with energy errors ofhundreds of cm~(-1)hundredths eV,r_eerrors of thousandths A, and ω_under 20 cm~(-1).Two kinds of interplay between SOC effect and bonding process (antibonding and bonding SOC)were demonstrated using spin-free term potential curves of PbH and BiH. The present study is thefirst extension of the model core potential method beyond Breit–Pauli to Douglas–Kroll SOC.
机译：已经建立了一种模型核心势能理论，该理论可以在道格拉斯—克罗尔形式主义的水平上处理自旋轨道耦合（SOC）效应。通过将运动学算子在道格拉斯-克罗尔自旋轨道算子中的阻尼效应存储到一组附加的基集收缩系数中，GAMESS-US程序中的Breit-Pauli自旋轨道代码被成功用于执行道格拉斯-科罗尔自旋轨道计算。发现在价轨道的径向函数中的微小误差导致自旋轨道能级的大误差，因此在模型核心势参数化中需要拟合自旋轨道矩阵元素的径向部分。针对两个6p嵌段元素Pb和Bi开发了包括新形式主义在内的第一个模型核心潜力。由于5p和6p轨道之间的SOC较大，因此使用了5p，5d，6s和6p轨道的化合价空间。在计算原子特性以及双原子金属氢化物的光谱常数时验证了模型的核心电势。模型核心势的结果与全电子计算结果之间的一致性极好，能量误差为几百cm〜（-1）百分之一eV，r_误差为千分之一A，ω_低于20 cm〜（-1）。两种相互作用使用PbH和BiH的无自旋项电位曲线证明了SOC效应和键合过程（抗键合和SOC）。本研究是模型核心潜力方法从Breit-Pauli扩展到Douglas-Kroll SOC的首次扩展。

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