A discussion on the relativistic corrections of the electronic structures of multi‐electron atoms

Abstract

AbstractThe theory of special relativity is a topic not addressed in theoretical chemistry courses. Einstein's theory of relativity is mainly applied to high‐energy phenomena governed by physical laws not used to describe the chemical bond. Nevertheless, the electrons of heavy elements orbit around the nucleus with relativistic velocities. Here it is, then, the laws that appeared so unusual for chemistry became fundamental tools for investigating the properties of these atoms. Studying the electronic structure of heavy elements is the best place for chemists to learn to tame the pitfalls of a little‐known subject, such as Einstein's theory, and become familiar with its elegant formalism. In this paper, the main relativistic approaches to quantum chemistry are revisited. The problem of the finite nuclear size, the approximation methods used to solve the relativistic equations for k‐shell electrons, and the problem of the negative energy continuum are investigated. Some ansatzes to solve divergence's problem of relativistic corrections near the nucleus are proposed. Finally, a possible connection between the self‐consistent field method and bondonic chemistry is also investigated.