Perturbation calculation of correlation energies for polyatomic molecules I. Initial results

The calculation of correlation energies for polyatomic molecules is discussed. Four second-order perturbation expressions are considered; only the simplest, a Rayleigh-Schroedinger expansion with the Moller-Plesset partitioning of the Hamiltonian is invariant to an arbitrary mixing of degenerate orbitals and has the correct dependence on the number of particles. In the absence of degeneracies an iterative Brillouin-Wigner method is proposed. Calculations predict that correlation effects favor the non-classical form of carbonium ions.