Asymptotics of the exchange splitting energy for a diatomic molecular ion from a volume integral formula of symmetry-adapted perturbation theory (1406.1905v2)

Abstract: The exchange splitting energy $J$ of the lowest \emph{gerade} and \emph{ungerade} states of the H$_2^+$ molecular ion was calculated using a volume integral expression of symmetry-adapted perturbation theory and standard basis set techniques of quantum chemistry. The performance of the proposed expression was compared to the well known surface integral formula. Both formulas involve the primitive function which we calculated employing either the Hirschfelder-Silbey perturbation theory or the conventional Rayleigh-Schr\"odinger perturbation theory (the polarization expansion). Our calculations show that very accurate values of $J$ can be obtained using the proposed volume integral formula. When the Hirschfelder-Silbey primitive function is used in both formulas the volume formula gives much more accurate results than the surface integral expression. We also show that using the volume integral formula with the primitive function approximated by Rayleigh-Schr\"odinger perturbation theory, one correctly obtains only the first four terms in the asymptotic expansion of the exchange splitting energy.