Nonrelativistic molecular quantum mechanics without approximations: Electron affinities of LiH and LiD

Abstract

We took the complete nonrelativistic Hamiltonians for the LiH and LiH2 systems, as well as their deuterated isotopomers, we separated the kinetic energy of the center of mass motion from the Hamiltonians, and with the use of the variational method we optimized the ground-state nonadiabatic wave functions for the systems expanding them in terms of n-particle explicitly correlated Gaussian functions. With 3600 functions in the expansions we obtained the lowest ever ground-state energies of LiH, LiD, LiH2, and LiD2 and these values were used to determine LiH and LiD electrons affinities ~EAs! yielding 0.330 30 and 0.327 13 eV, respectively. The present are the first high-accuracy ab initio quantum mechanical calculations of the LiH and LiD EAs that do not assume the Born-Oppenheimer approximation. The obtained EAs fall within the uncertainty brackets of the experimental results