A b i n i t i o study of the electronic structure of Li2 −

Abstract

We have performed SCF–CI calculations on the ground states of Li₂ and its anion. We predict a value aof 0.45 eV for the adiabatic electron affinity of Li₂ and a value of 0.86 eV for the dissociation energy of Li₂ ⁻. Thus, the bond strength of the anion is nearly the same as that of the neutral parent. This indicates that the simple MO picture, describing the anion as being formed by the addition of an electron to the antibonding 2σ_u orbital, is not adequate. The present results are compared to the recent equation‐of‐motion calculation of the Li₂ electron affinity by Andersen and Simons.