Towards a double many-body expansion method for multivalued potential energy surfaces

Abstract

Using the diatomics-in-molecules formalism to get a first-order potential matrix, an extension is proposed of the double many-body expansion (DMBE) method for multivalued potential energy surfaces. The method consists of dressing the diatomic states with many-body energy terms of the extended Hartree-Fock and dynamical correlation type, with spin-recoupling and orientational effects being treated as in the traditional diatomics-in-molecules approach. All states of the polyatomic dissociate properly. Examples are discussed for s3, s2p, and sp2 systems. Specifically, a DMBE potential energy surface is reported for NO2 which shows the correct energy and geometry at the equilibrium structure and is in fair agreement with ab initio calculations at other regions of configuration space. Thus, this NO2 potential energy surface may be useful for molecular dynamics studies.