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

Abstract

The conventional surface integral formula $J_{\mathrm{surf}}[\Phi ]$ and an alternative volume integral formula $J_{\mathrm{var}}[\Phi ]$ are used to compute the asymptotic exchange splitting of the interaction energy of the hydrogen atom and a proton employing the primitive function $\Phi$ in the form of its truncated multipole expansion. Closed-form formulas are obtained for the asymptotics of $J_{\mathrm{surf}}[{\Phi }_N]$ and $J_{\mathrm{var}}[{\Phi }_N]$, where ${\Phi }_N$ is the multipole expansion of $\Phi$ 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 $J_{\text{var}}[\Phi ]$. At low order the observed convergence of $J_{\mathrm{var}}[{\Phi }_N]$ 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.

arXiv comment20 pages, 2 figures (incl. graphical abstract), submitted to Molecular Physics

References in corpus (1)

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

Cited by in corpus (1)

• Determination of the exchange interaction energy from the polarization expansion of the wave function