Second-Order Dispersion Energy Based on Multireference Description of Monomers

We propose a method for calculating a second-order dispersion energy for weakly interacting multireference systems in arbitrary electronic states. It is based on response properties obtained from extended random phase approximation equations. The introduced formalism is general and requires only one- and two-particle reduced density matrices of monomers. We combine the new method with either generalized valence bond perfect pairing (GVB) or complete active space (CAS) self-consistent field description of the interacting systems. In addition to a general scheme, three approximations, leading to significant reduction of the computational cost, are developed by exploiting Dyall partitioning of the monomer Hamiltonians. For model multireference systems (H2···H2 and Be···Be) the method is accurate, unlike its single-reference-based counterpart. Neither GVB nor CAS description of single-reference monomers improves the dispersion energy with respect to the Hartree–Fock-based results.