Varying Electronic Configurations in Compressed Atoms: From the Role of the Spatial Extension of Atomic Orbitals to the Change of Electronic Configuration as an Isobaric Transformation.
Roberto CammiMartin RahmRoald HoffmannN W AshcroftPublished in: Journal of chemical theory and computation (2020)
A quantum chemical model for the study of the electronic structure of compressed atoms lends itself to a perturbation-theoretic analysis. It is shown, both analytically and numerically, that the increase of the electronic energy with increasing compression depends on the electronic configuration, as a result of the variable spatial extent of the atomic orbitals involved. The different destabilization of the electronic states may lead to an isobaric change of the ground-state electronic configuration, and the same first-order model paves the way to a simple thermodynamical interpretation of this process.