Analytical energy gradients for ionized states using equation-of-motion coupled-cluster theory with spin-orbit coupling.

Abstract

Spin-orbit coupling (SOC) may have a significant effect on the structure and harmonic frequencies of particularly heavy p-block element compounds. However, reports on analytical energy gradients with SOC are scarce, especially for excited states. In this work, we implemented analytical energy gradients for ionized states using the equation-of-motion coupled-cluster (CC) theory at the CC singles and doubles level (EOM-IP-CCSD) with SOC. Effects of SOC on structure and harmonic frequencies as well as properties for both the ground and some excited states of open-shell compounds with one unpaired electron can be investigated efficiently with the present implementation. A closed-shell reference is required in the calculations, and SOC is included in post-Hartree-Fock treatment. Relativistic effective core potentials are employed in dealing with both scalar relativistic effects and SOC, and we treat perturbations that are even under time reversal in this work. Both time-reversal symmetry and double point group symmetry for D2h * and its subgroups are exploited in the implementation. The method is applicable to states which can be reached by removing one electron from a closed-shell reference state. The results of some open-shell cations indicate the importance of SOC on structures and harmonic frequencies of heavy element compounds.