Consistent Second-Order Treatment of Spin–Orbit Coupling and Dynamic Correlation in Quasidegenerate N-Electron Valence Perturbation Theory

Abstract

We present a formulation and implementation of second-order quasidegenerate N-electron valence perturbation theory (QDNEVPT2) that provides a balanced and accurate description of spin–orbit coupling and dynamic correlation effects in multiconfigurational electronic states. In our approach, the energies and wave functions of electronic states are computed by treating electron repulsion and spin–orbit coupling operators as equal perturbations to the nonrelativistic complete active-space wave functions, and their contributions are incorporated fully up to the second order. The spin–orbit effects are described using the Breit–Pauli (BP) or exact two-component Douglas–Kroll–Hess (DKH) Hamiltonians within spin–orbit mean-field approximation. The resulting second-order methods (BP2- and DKH2-QDNEVPT2) are capable of treating spin–orbit coupling effects in nearly degenerate electronic states by diagonalizing an effective Hamiltonian expanded in a compact non-relativistic basis. For a variety of atoms and small molecules across the entire periodic table, we demonstrate that DKH2-QDNEVPT2 is competitive in accuracy with variational two-component relativistic theories. BP2-QDNEVPT2 shows high accuracy for the second- and third-period elements, but its performance deteriorates for heavier atoms and molecules. We also consider the first-order spin–orbit QDNEVPT2 approximations (BP1- and DKH1-QDNEVPT2), among which DKH1-QDNEVPT2 is reliable but less accurate than DKH2-QDNEVPT2. Both DKH1- and DKH2-QDNEVPT2 hold promise as efficient and accurate electronic structure methods for treating electron correlation and spin–orbit coupling in a variety of applications.