Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

Prachi Sharma

doi:10.1021/acs.jctc.2c00062

Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

2022-04-06

18

PRE

AI

DOI：10.1021/acs.jctc.2c00062

Original

Original request for help

Save

Abstract

En 中文

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

Keywords:

2ND-ORDER PERTURBATION-THEORY

GRADIENT APPROXIMATION

OPEN-SHELL

CHEMISTRY

STATE

CHALLENGES

MOLECULES

SYSTEMS

Exact-Two-Component Multiconfiguration Pair-Density Functional Theory

Abstract

Journal

Organization