Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

Abstract

Molecules containing late-row elements exhibit large relativistic effects. To account for both relativistic effects and electron correlation in a computationally inexpensive way, we derived a formulation of multiconfiguration pair-density functional theory with the relativistic exact-two-component Hamiltonian (X2C-MC-PDFT). In this new method, relativistic effects are included during variational optimization of a reference wave function by exact-two-component complete active-space self-consistent-field (X2C-CASSCF) theory, followed by an energy evaluation using pair-density functional theory. Benchmark studies of excited-state and ground-state fine-structure splitting of atomic species show that X2C-MC-PDFT can significantly improve the X2C-CASSCF results by introducing additional state-specific electron correlation.