THE HYLLERAAS BINDING ENERGY OF HYDRIDE AND ELECTRON AFFINITIES

Abstract

The normalized electron affinity of the hydrogen atom, is the fundamental measure of anionic electron correlation. The three-body H (−) and AB(−) systems analogous to Efimov three-body bosons support multiple excited states. The first complete set of ground state electron affinities of the main group atoms and homonuclear diatomic molecules are reported using the Hylleraas variational binding energy of the hydride anion. Thermal electron affinities and activation energies for the formation of the 27 bonding states of O2(−) are reported from electron capture detector and atmospheric pressure negative ion mass spectrometry. These are iterated through magnetron, flame, swarm, electron impact, photodetachment, and negative ion photoelectron spectra to obtain more precise self-consistent values. Electron affinities for NO are similarly reported. These data are used to calculate Herschbach ionic Morse Person electron curves for the 54 O2(−) and 87 NO (−) states predicted by adiabatic correlation rules. A new ground state adiabatic electron affinity of SF63.00(10) eV is determined from negative ion mass spectra.