Dirac-Coulomb-Breit Molecular Mean-Field Exact-Two-Component Relativistic Equation-of-Motion Coupled-Cluster Theory

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作   者：

Zhang, Tianyuan;  Banerjee, Samragni;  Koulias, Lauren N.;  Valeev, Edward F.;  DePrince, A. Eugene;  Li, Xiaosong; 

作者机构：

Univ Washington;  Florida State Univ; 

关键词：

TRANSITION;  EXCITATION-ENERGIES;  GROUND-STATE;  NONRELATIVISTIC METHODS;  DENSITY-FUNCTIONAL-THEORY;  ELECTRON ATTACHED STATES;  BASIS-SETS;  OPEN-SHELL;  GOLD ATOM;  NORMALIZED ELIMINATION; 

期刊名称：

The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory

i s s n：

1089-5639

年卷期：

2024 年 128 卷 17 期

页   码：

3408-3418

页   码：

摘   要：

We present a relativistic equation-of-motion coupled-cluster with single and double excitation formalism within the exact two-component framework (X2C-EOM-CCSD), where both scalar relativistic effects and spin-orbit coupling are variationally included at the reference level. Three different molecular mean-field treatments of relativistic corrections, including the one-electron, Dirac-Coulomb, and Dirac-Coulomb-Breit Hamiltonian, are considered in this work. Benchmark calculations include atomic excitations and fine-structure splittings arising from spin-orbit coupling. Comparison with experimental values and relativistic time-dependent density functional theory is also carried out. The computation of the oscillator strength using the relativistic X2C-EOM-CCSD approach allows for studies of spin-orbit-driven processes, such as the spontaneous phosphorescence lifetime.