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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.

journal of chemical theory and computation

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