Efficient Calculation of the Dispersion Energy for Multireference Systems with Cholesky Decomposition: Application to Excited-State Interactions

Abstract

Accurate and efficient prediction of dispersion interactions in excited-state complexes poses a challenge due to the complex nature of electron correlation effects that need to be simultaneously considered. We propose an algorithm for computing the dispersion energy in nondegenerate ground- or excited-state complexes with arbitrary spin. The algorithm scales with the fifth power of the system size due to employing Cholesky decomposition of Coulomb integrals and a recently developed recursive formula for density response functions of the monomers. As a numerical illustration, we apply the new algorithm in the framework of multiconfigurational symmetry adapted perturbation theory, SAPT(MC), to study interactions in dimers with localized excitons. The SAPT(MC) analysis reveals that the dispersion energy may be the main force stabilizing excited-state dimers.