Convergence properties of the multipole expansion of the exchange contribution to the interaction energy

Abstract

The conventional surface integral formula $J_{\rm surf}[Φ]$ and an alternative volume integral formula $J_{\rm var}[Φ]$ are used to compute the asymptotic exchange splitting of the interaction energy of the hydrogen atom and a proton employing the primitive function $Φ$ in the form of its truncated multipole expansion. Closed-form formulas are obtained for the asymptotics of $J_{\rm surf}[Φ_N]$ and $J_{\rm var}[Φ_N]$, where $Φ_N$ is the multipole expansion of $Φ$ truncated after the $1/R^N$ term, $R$ being the internuclear separation. It is shown that the obtained sequences of approximations converge to the exact results with the rate corresponding to the convergence radius equal to 2 and 4 when the surface and the volume integral formulas are used, respectively. When the multipole expansion of a truncated, $K$th order polarization function is used to approximate the primitive function the convergence radius becomes equal to unity in the case of $J_{\textrm{var}}[Φ]$. At low order the observed convergence of $J_{\rm var}[Φ_N]$ is, however, geometric and switches to harmonic only at certain value of $N=N_c$ dependent on $K$. An equation for $N_c$ is derived which very well reproduces the observed $K$-dependent convergence pattern. The results shed new light on the convergence properties of the conventional SAPT expansion used in applications to many-electron diatomics.