Relativistic Effects in Chemical Bonding: The H2+ Molecule

Abstract

The behavior of the electron in the ground state of the hydrogen molecular ion is examined using the Dirac theory. Since the resulting set of equations is not readily separable, the variational theorem is applied to obtain approximate eigenfunctions for the ground state. Trial variational functions having the same symmetry properties as the exact solution can be conceptualized as a superposition of functions closely resembling nonrelativistic molecular orbitals. The relativistic correction to the electronic energy is approximately −7×10−6 a.u