Single-Configuration Wavefunctions and Potential Curves for Low-Lying States of He2+, Ne2+, Ar2+, F2−, Cl2− and the Ground State of Cl2

Abstract

Wavefunctions, orbital energies, and potential curves for ${\mathrm{He}}_2^{+}\mathrm{,\hspace{0.17em}}{\mathrm{Ne}}_2^{+}\mathrm{,\hspace{0.17em}}{\mathrm{Ar}}_2^{+}\mathrm{,\hspace{0.17em}}{\mathrm{F}}_2^{-}$ , and ${\mathrm{Cl}}_2^{-}$ have been calculated in the molecular‐orbital, self‐consistent‐field approximation over a range $R_e\mathrm{\lesssim \; R\; <\; \infty }$ for the ground state and those excited states which dissociate into an atom and an ion in their ground states. The ground state potential curve for Cl₂ has been calculated for ${\mathrm{R\; \sim \; R}}_e$ . Dissociation energies and other parameters obtained from the calculated potential curves are compared with corresponding parameters obtained from elastic differential scattering measurements and resonant electron capture in noble gases, measurements of afterglow line profiles in dissociative recombination radiation in neon and argon, optical absorption spectra of V_K centers, and endoergic charge transfer studies of halogen ions and molecules. A formal analysis and discussion of the sources of correlation error in the calculated potential curves and a discussion of the expansion errors are also given.