Combining pair-density functional theory and variational two-electron reduced-density matrix methods

TL;DR

This paper introduces a combined computational approach using variational two-electron reduced-density matrix methods and on-top pair-density functional theory to efficiently describe both static and dynamical electron correlation in complex systems.

Contribution

The paper develops and applies a novel v2RDM-CASSCF-PDFT method that integrates active-space RDM optimization with density functional theory for improved correlation modeling.

Findings

Successfully applied to potential energy curves of N2, H2O, and CN-

Estimated singlet/triplet splitting in long acenes as 4.87 kcal/mol

Demonstrated computational efficiency in multiconfigurational systems

Abstract

Complete active space self-consistent field (CASSCF) computations can be realized at polynomial cost via the variational optimization of the active-space two-electron reduced-density matrix (2-RDM). Like conventional approaches to CASSCF, variational 2-RDM (v2RDM)-driven CASSCF captures nondynamical electron correlation in the active space, but it lacks a description of the remaining dynamical correlation effects. Such effects can be modeled through a combination of v2RDM-CASSCF and on-top pair-density functional theory (PDFT). The resulting v2RDM-CASSCF-PDFT approach provides a computationally inexpensive framework for describing both static and dynamical correlation effects in multiconfigurational and strongly correlated systems. On-top pair-density functionals can be derived from familiar Kohn-Sham exchange-correlation (XC) density functionals through the translation of the v2RDM-CASSCF reference densities [Li Manni et al., J. Chem. Theory Comput. 10, 3669-3680 (2014)]. Translated and fully-translated on-top PDFT versions of several common XC functionals are applied to the potential energy curves of N2, H2O, and CN-, as well as to the singlet/triplet energy splittings in the linear polyacene series. Using v2RDM-CASSCF-PDFT and the translated PBE functional, the singlet/triplet energy splitting of an infinitely-long acene molecule is estimated to be 4.87 kcal/mol.