Small-Occupation Density Functional Correlation Energy Correction to Wave Function Approximations.

Abstract

In this work, we introduce a novel hybrid approach, termed WFT-soDFT, designed to seamlessly incorporate DFT correlation into wave function ansatzes. This is achieved through a partitioning of the orbital space, distinguishing between large and small natural occupation numbers associated with wave function theory (WFT) and DFT correlation, respectively. The method uses a novel criterion for partitioning the orbital space and mapping the electron density in natural orbitals with a small occupation with the correlation energy of fast electrons within the homogeneous electron gas. Central to our approach is the introduction of a separation parameter ν, the choice of the WFT approach, and the correlation functional. Here, we combine the RASCI wave function with hole and particle truncation with a local density correlation functional to only account for small-occupation correlation energy. We investigate the performance of the method in the study of small but challenging chemical systems, for which WFT-soDFT demonstrates notable improvements over pristine wave function calculations. These findings collectively highlight the potential of the WFT-soDFT approach as a computationally affordable strategy to improve the accuracy of WFT electronic structure calculations.