How Much Dispersion Energy Is Included in the Multiconfigurational Interaction Energy?

J Chem Theory Comput. 2020 Oct 13;16(10):6280-6293. doi: 10.1021/acs.jctc.0c00681. Epub 2020 Sep 18.

Abstract

We demonstrate how to quantify the amount of dispersion interaction recovered by supermolecular calculations with the multiconfigurational self-consistent field (MCSCF) wave functions. For this purpose, we present a rigorous derivation which connects the portion of dispersion interaction captured by the assumed wave function model-the residual dispersion interaction-with the size of the active space. Based on the obtained expression for the residual dispersion contribution, we propose a dispersion correction for the MCSCF that avoids correlation double counting. Numerical demonstration for model four-electron dimers in both ground and excited states described with the complete active space self-consistent field (CASSCF) reference serves as a proof-of-concept for the method. Accurate results, largely independent of the size of the active space, are obtained. For many-electron systems, routine CASSCF interaction energy calculations recover a tiny fraction of the full second-order dispersion energy. We found that the residual dispersion is non-negligible only for purely dispersion-bound complexes.