Perturbation calculation of the interaction energy using orthogonalized orbitals

Abstract.

The diagrammatic Rayleigh-Schrödinger perturbation theory for the interaction of two closed-shell systems is developed up to the third order of pertur-bation using orthogonalized orbitals. The interaction energy is expressed by the Rayleigh-Schrödinger perturbation expansion. A simple approach for the estimation of basis set superposition error is introduced. The preliminary calculations of the intermolecular interactions for the He dimer within the augmented cc-pVTZ basis set are compared with the supermolecular approach, perturbation calculation in biorthogonal basis sets and symmetry adapted perturbation theory results.