density functional

perturbation theory

potential energy

matrix elements

electronic states

wave functions

Journal of Chemical Theory and Computation

As the relativistic corrections become stronger for late-row elements, the fully perturbative treatment of spin-orbit coupling and dynamic correlation may become inadequate for accurate descriptions of chemical properties. In this work, we introduce a determinant-based Kramers-unrestricted exact-two-component multireference second-order perturbation (X2C-MRPT2) method which variationally includes relativistic corrections with a perturbative dynamic correlation. The restricted active space partitioning scheme is employed to provide an adjustable correlation space for the second-order perturbation treatment. The multistate perturbation theory is also developed to improve the descriptions of ground and excited states. Benchmark studies of atomic fine-structure splittings and spectroscopic constants of molecular monohydrides using X2C-MRPT2 are compared to the other perturbative and variational approaches. The results suggest that X2C-MRPT2 is a highly accurate alternative to the fully variational multireference configuration interaction method at only a small fraction of the computational cost.

Exact-Two-Component Relativistic Multireference Second-Order Perturbation Theory