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Franck–Condon theory of quantum mechanochemistry


Rybkin, Vladimir V (2017). Franck–Condon theory of quantum mechanochemistry. Journal of Physical Chemistry. A, 121(30):5758-5762.

Abstract

The spectroscopic Franck-Condon (FC) principle is extended to mechanochemistry. If the external force is applied rapidly (the sudden-force regime), then the transition between the potential energy surface and the force-modified potential energy surface is analogous to the optical electronic transition. Such a transition produces a nonequilibrium ensemble of vibrationally excited molecules. This excess of vibrational energy is another activation source in addition to the well-known reaction barrier modulation by the external force. In the same time, the nonequilibrium vibrational distribution implies nonstatistical kinetics of a mechanochemical transformation. Mechanochemical FC principle thus provides a conceptual picture for the sudden-force mechanochemistry and opens possibilities for quantitative calculations of the mechanochemical rates and mechanisms. Here we use it to compute the dissociation rates of a model diatomic molecule and to explain the selectivity in mechanochemical bond breaking in n-butane. The approach is predicted to be relevant for large-magnitude external forces, applied instantaneously. Otherwise, the excess vibrational energy will dissipate due to intramolecular vibrational redistribution and interaction with environment.

Abstract

The spectroscopic Franck-Condon (FC) principle is extended to mechanochemistry. If the external force is applied rapidly (the sudden-force regime), then the transition between the potential energy surface and the force-modified potential energy surface is analogous to the optical electronic transition. Such a transition produces a nonequilibrium ensemble of vibrationally excited molecules. This excess of vibrational energy is another activation source in addition to the well-known reaction barrier modulation by the external force. In the same time, the nonequilibrium vibrational distribution implies nonstatistical kinetics of a mechanochemical transformation. Mechanochemical FC principle thus provides a conceptual picture for the sudden-force mechanochemistry and opens possibilities for quantitative calculations of the mechanochemical rates and mechanisms. Here we use it to compute the dissociation rates of a model diatomic molecule and to explain the selectivity in mechanochemical bond breaking in n-butane. The approach is predicted to be relevant for large-magnitude external forces, applied instantaneously. Otherwise, the excess vibrational energy will dissipate due to intramolecular vibrational redistribution and interaction with environment.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2017
Deposited On:11 Dec 2017 15:53
Last Modified:19 Feb 2018 09:09
Publisher:American Chemical Society (ACS)
ISSN:1089-5639
OA Status:Closed
Publisher DOI:https://doi.org/10.1021/acs.jpca.7b06565
PubMed ID:28685567

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