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

J Phys Chem A. 2024 May 2;128(17):3408-3418. doi: 10.1021/acs.jpca.3c08167. Epub 2024 Apr 23.

Abstract

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.