On boundedness of isomerization paths for non- and semirelativistic molecules

TL;DR

This paper proves that the distance between submolecules remains bounded during isomerization reactions under certain conditions, extending previous work to include semirelativistic effects and relaxed assumptions.

Contribution

It generalizes prior results by allowing semirelativistic kinetic energy and relaxing ground state eigenspace assumptions in the analysis of isomerization paths.

Findings

Boundedness of submolecule distance during reactions

Asymptotic expansion of interaction energy including multipolar and van der Waals terms

Extension to semirelativistic kinetic energy and relaxed assumptions

Abstract

This article focuses on isomerizations of molecules, i.e. chemical reactions during which a molecule is transformed into another one with the same atoms in a different spatial configuration. We consider the special case in which the system breaks into two submolecules whose internal geometry is solid during the whole procedure. We prove, under some conditions, that the distance between the two submolecules stays bounded during the entire reaction. To this end, we provide an asymptotic expansion of the interaction energy between two molecules, including multipolar interactions and the van der Waals attraction. In addition to this static result, we proceed to a quasistatic analysis to investigate the variation of the energy when the nuclei move. This paper generalizes a recent work by M. Lewin and the first author in two directions. The first one is that we relax the assumption that the ground state eigenspaces of the submolecules have to fulfill. The second one is that we allow semirelativistic kinetic energy as well.