Variational solution of the dirac equation within a multicentre basis set of gaussian functions

Abstract

The Dirac equation for one-electron polynuclear systems is solved variationally within an analytical multicentre basis set. Each of the four components of the molecular spinor is expanded separately into a scalar basis set. The expansion coefficients are obtained from the variational principle. Calculations using gaussian functions are performed for hydrogen-like atoms and for hydrogen-ion-like molecules with constituents of nuclear charge Z = 1, 50 and 90.