A Cost-Effective Treatment of Spin-Orbit Couplings in the State-Averaged Driven Similarity Renormalization Group Second-Order Perturbation Theory.

Abstract

We present an economical approach to treat spin-orbit coupling (SOC) in the state-averaged driven similarity renormalization group second-order perturbation theory (SA-DSRG-PT2). The electron correlation is first introduced by forming the SA-DSRG-PT2 dressed spin-free Hamiltonian. This Hamiltonian is then augmented with the Breit-Pauli Hamiltonian and diagonalized using spin-pure reference states to obtain the SOC-corrected energy spectrum. The spin-orbit mean-field approximation is also assumed to reduce the cost associated with the two-electron spin-orbit integrals. The resulting method is termed BP1-SA-DSRG-PT2c, and it possesses the same computational scaling as the non-relativistic counterpart, where only the one- and two-body density cumulants are required to obtain the vertical transition energy. The accuracy of BP1-SA-DSRG-PT2c is assessed on a few atoms and small molecules, including main-group diatomic molecules, transition-metal atoms, and actinide dioxide cations. Numerical results suggest that BP1-SA-DSRG-PT2c performs comparably to other internally contracted multireference perturbation theories with SOC treated using the state interaction scheme.