Semiclassical Dispersion Corrections efficiently improve Multi-Configurational Theory with Short-Range Density-Functional Dynamic Correlation

TL;DR

This paper introduces a hybrid method combining multi-configurational wave functions with short-range DFT and semiclassical dispersion corrections, achieving accurate reaction energies efficiently without double counting.

Contribution

It proposes a novel MC-srDFT-D hybrid approach that efficiently incorporates long-range dispersion and short-range dynamical correlation in multi-configurational theory.

Findings

The method provides reliable reaction energy calculations.

It achieves this with negligible computational cost.

It corrects overestimations common in second-order multi-reference perturbation theory.

Abstract

Multi-configurational wave functions are known to describe electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamical correlation originating from the many configurations involving excitations out of the restricted orbital space, the active space, must be considered. Standard procedures involve approximations that eventually limit the ultimate accuracy achievable (most prominently, multi-reference perturbation theory). At the same time, the computational cost increase dramatically due to the necessity to obtain higher-order reduced density matrices. It is this disproportion that leads us here to propose a MC-srDFT-D hybrid approach of semiclassical dispersion (D) corrections to cover long-range dynamical correlation in a multi-configurational (MC) wave function theory which includes short-range (sr) dynamical correlation by density functional theory (DFT) without double counting. We demonstrate that the reliability of this approach is very good (at negligible cost), especially when considering that standard second-order multi-reference perturbation theory usually overestimates dispersion interactions.