Semiclassical Dispersion Corrections Efficiently Improve Multiconfigurational Theory with Short-Range Density-Functional Dynamic Correlation.

ABSTRACT

Multiconfigurational wave functions are known to describe the electronic structure across a Born-Oppenheimer surface qualitatively correct. However, for quantitative reaction energies, dynamic 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, multireference perturbation theory). At the same time, the computational cost increases dramatically due to the necessity to obtain higher-order reduced density matrices. It is this disproportion that leads us here to propose an MC-srDFT-D hybrid approach of semiclassical dispersion (D) corrections to cover long-range dynamic correlation in a multiconfigurational (MC) wave function theory, which includes short-range (sr) dynamic 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 multireference perturbation theory usually overestimates dispersion interactions.