State Interaction for Relativistic Four-Component Methods: Choose the Right Zeroth-Order Hamiltonian for Late-Row Elements,Journal of Chemical Theory and Computation

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State Interaction for Relativistic Four-Component Methods: Choose the Right Zeroth-Order Hamiltonian for Late-Row Elements
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-09-10 , DOI: 10.1021/acs.jctc.4c00797
Chad E Hoyer ₁ , Can Liao ₁ , Kirill D Shumilov ₁ , Tianyuan Zhang ₁ , Xiaosong Li ₁

Affiliation

We present several schemes based on the spin-separation of the Dirac–Coulomb–Breit Hamiltonian for the perturbative treatment of relativistic four-component Hamiltonians within the state interaction framework. While state interaction approaches traditionally use zeroth-order scalar-relativistic states, we develop augmented zeroth-order Hamiltonians with increasing accuracy and investigate convergence to the variational limit as a function of the choice of zeroth-order Hamiltonian. The state interaction schemes developed in this work are benchmarked using ground-state fine-structure splitting of late-row atoms and diatomic hyrides. Although the scalar-relativistic zeroth-order Hamiltonian exhibits significant errors in ground-state fine-structure splitting, the predictive accuracy can be improved by augmenting the zeroth-order Hamiltonian with one- and two-electron vector-relativistic operators (e.g., spin–orbit, spin–spin, orbit–orbit). This work lays the theoretical foundation for the development of low-scaling, high-accuracy perturbative relativistic methods suitable for late-row elements.

中文翻译：

相对论四分量方法的状态相互作用：为后行元素选择正确的零阶哈密顿量

我们提出了几种基于狄拉克-库仑-布莱特哈密顿量的自旋分离的方案，用于在状态相互作用框架内对相对论四分量哈密顿量进行微扰处理。虽然状态相互作用方法传统上使用零阶标量相对论状态，但我们开发了精度不断提高的增强零阶哈密顿量，并研究了作为零阶哈密顿量选择的函数向变分极限的收敛性。这项工作中开发的状态相互作用方案使用后排原子和双原子氢化物的基态精细结构分裂进行基准测试。尽管标量相对论零阶哈密顿量在基态精细结构分裂中表现出显着误差，但可以通过用一电子和二电子矢量相对论算子（例如自旋-轨道、自旋-自旋、轨道-轨道）。这项工作为开发适用于后排元素的低尺度、高精度微扰相对论方法奠定了理论基础。

更新日期：2024-09-10

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