title: Equation-of-Motion Coupled-Cluster Theory for Excitation Energies of Closed-Shell Systems with Spin-Orbit Coupling.
abstract: Excitation energies of closed-shell systems based on the equation-of-motion (EOM) coupled-cluster theory at the singles and doubles (CCSD) level with spin-orbit coupling (SOC) included in the post-Hartree-Fock treatment are implemented in the present work. SOC can be included in both the CC and EOM steps (EOM-SOC-CCSD) or only in the EOM part (SOC-EOM-CCSD). The latter approach is an economical way to account for SOC effects, but excitation energies with this approach are not size-intensive. When the unlinked term in the latter approach is neglected (cSOC-EOM-CCSD), size-intensive excitation energies can be obtained. Time-reversal symmetry and spatial symmetry are exploited to reduce the computational effort. Imposing time-reversal symmetry results in a real matrix representation for the similarity-transformed Hamiltonian, which facilitates the requirement of time-reversal symmetry for new trial vectors in Davidson's algorithm. Results on some closed-shell atoms and molecules containing heavy elements show that EOM-SOC-CCSD can provide excitation energies and spin-orbit splittings with reasonable accuracy. On the other hand, the SOC-EOM-CCSD approach is able to afford accurate estimates of SOC effects for valence electrons of systems containing elements up to the fifth row, while cSOC-EOM-CCSD is less accurate for spin-orbit splittings of transitions involving p1/2 spinors, even for Kr.
authors.affiliation: Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610064, P. R. China.
authors.forename: Zhifan
authors.initials: Z
authors.lastname: Wang
authors.affiliation: School of Science, Xi'an Polytechnic University , Xi'an, Shaanxi 710048, P. R. China.
authors.forename: Zheyan
authors.initials: Z
authors.lastname: Tu
authors.affiliation: Institute of Atomic and Molecular Physics, Sichuan University , Chengdu 610064, P. R. China.
authors.forename: Fan
authors.initials: F
authors.lastname: Wang