Relativistic variational methods and the Virial Theorem

Abstract

In the case of the one-electron Dirac equation with a point nucleus the Virial Theorem (VT) states that the ratio of the kinetic energy to potential energy is exactly −1, a ratio that can be an independent test of the accuracy of a computed solution. This paper studies the virial theorem for subshells of equivalent electrons and their interactions in many-electron atoms. It shows that some Slater integrals impose conditions on a single subshell but others impose conditions between subshells. The latter slow the rate of convergence of the self-consistent field process in which radial functions are updated one at a time. Several cases are considered.