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

TL;DR

This paper derives and tests a volume integral formula for calculating the exchange splitting energy in H₂⁺, showing it outperforms the surface integral method when using certain primitive functions, especially asymptotically.

Contribution

The paper introduces a volume integral expression for exchange splitting energy and demonstrates its superior accuracy over the surface integral formula in quantum chemistry calculations.

Findings

Volume integral formula yields highly accurate exchange splitting energies.

Using Hirschfelder-Silbey primitive functions enhances accuracy significantly.

Asymptotic expansion is correctly captured up to four terms with Rayleigh-Schrödinger primitive functions.

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.