Properties of Relativistic Mean-Field Theory

We have previously seen how the Dirac equation for one particle requires some rather special consideration and interpretation in order to arrive at a form that is able to treat electrons and positrons on an equal footing. These problems persist also when we go to systems with more than one electron. One might think that the extension to several electrons should not introduce dramatic changes. After all, we noted that even the one-electron problem must be viewed as a many-electron (and -positron) system in order to arrive at a consistent description. The problem with introducing more electrons is that electron–electron interactions that were previously small—for the one-electron case typically arising from vacuum polarization and self-interaction—now occur to the same order as the kinetic energy and the interaction with the potential. So while a perturbative approach such as QED can use the solutions of the one-electron Dirac equations as a very good starting approximation to a more accurate description of the full system, the same would not work for a system with more electrons because it would mean neglecting interactions of the same magnitude as the zeroth-order energy. For applications to quantum chemistry, the treatment of the entire electron–electron interaction as a perturbation would be hopelessly impractical, as it is even in manyelectron relativistic atomic structure calculations. The technique for dealing with this problem is well known from nonrelativistic calculations on many-electron systems. One-particle basis sets are developed by considering the behavior of the single electron in the mean field of all the other electrons, and while this neglects a smaller part of the interaction energy, the electron correlation, it provides a suitable starting point for further variational or perturbational treatments to recover more of the electron–electron interaction. It is only natural to pursue the same approach for the relativistic case. Thus one may proceed to construct a mean-field method that can be used as a basis for the perturbation theory of QED.