Correspondence between the reaction force minimum and the onset of abrupt variations of the kinetic and potential energies in bond dissociation and formation.

Autor: Politzer P; Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA., Gutiérrez-Oliva S; Laboratorio de Química Teórica Computacional (QTC), Facultad de Química, Pontificia Universidad Cátolica de Chile, Casilla 306, Correo 22, Santiago, Chile., Clark T; Department of Chemistry and Pharmacy, Computer-Chemie-Centrum, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nägelsbachstr. 25, Erlangen, 91052, Germany., Murray JS; Department of Chemistry, University of New Orleans, New Orleans, LA, 70148, USA. jane.s.murray@gmail.com.
Jazyk: angličtina
Zdroj: Journal of molecular modeling [J Mol Model] 2024 Aug 06; Vol. 30 (9), pp. 300. Date of Electronic Publication: 2024 Aug 06.
DOI: 10.1007/s00894-024-06101-0
Abstrakt: Context: We demonstrate that the minimum of the reaction force curve of a diatomic or polyatomic molecule undergoing bond dissociation is significant in several respects. As has been pointed out in the past, it is the point at which the force opposing dissociation is strongest. It marks the boundary between the primarily structural stage of a bond dissociation (stretching) and the transition region between the stretched bond and independent atoms. We now show that the reaction force minimum is also where the kinetic and potential energy curves tend to change direction abruptly. At this point, the total energy E(R) has increased by about 27% of the dissociation energy, for both diatomic and polyatomic molecules.
Methods: Dissociation curves are analyzed at the UHF/daug-cc-pV5Z level of theory using Gaussian 16.
(© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)
Databáze: MEDLINE
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