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Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes

[Image: see text] In this article, we propose a simple method of estimating dissociation rates of bimolecular van der Waals complexes (“wells”), rooted in rigid body dynamics, requiring as input parameters only the bimolecular binding energy, together with the intermolecular equilibrium distance and...

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Autor principal: Franzon, Lauri
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10364079/
https://www.ncbi.nlm.nih.gov/pubmed/37418045
http://dx.doi.org/10.1021/acs.jpca.3c01890
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author Franzon, Lauri
author_facet Franzon, Lauri
author_sort Franzon, Lauri
collection PubMed
description [Image: see text] In this article, we propose a simple method of estimating dissociation rates of bimolecular van der Waals complexes (“wells”), rooted in rigid body dynamics, requiring as input parameters only the bimolecular binding energy, together with the intermolecular equilibrium distance and moments of inertia of the complex. The classical equations of motion are solved for the intermolecular and rotational degrees of freedom in a coordinate system considering only the relative motion of the two molecules, thus bypassing the question of whether the energy of the complex is statistically distributed. Well-escaping trajectories are modeled from these equations, and the escape rate as a function of relative velocity and angular momentum is fitted to an empirical function, which is then integrated over a probability distribution of said quantities. By necessity, this approach makes crude assumptions on the shape of the potential well and neglects the impact of energy quantization, and, more crucially, the coupling between the degrees of freedom included in the equations of motion with those that are not. We quantify the error caused by the first assumption by comparing our model potential with a quantum chemical potential energy surface (PES) and show that while the model does make several compromises and may not be accurate for all classes of bimolecular complexes, it is able to produce physically consistent dissociation rate coefficients within typical atmospheric chemistry confidence intervals for triplet state alkoxyl radical complexes, for which the detailed balance approach has been shown to fail.
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spelling pubmed-103640792023-07-25 Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes Franzon, Lauri J Phys Chem A [Image: see text] In this article, we propose a simple method of estimating dissociation rates of bimolecular van der Waals complexes (“wells”), rooted in rigid body dynamics, requiring as input parameters only the bimolecular binding energy, together with the intermolecular equilibrium distance and moments of inertia of the complex. The classical equations of motion are solved for the intermolecular and rotational degrees of freedom in a coordinate system considering only the relative motion of the two molecules, thus bypassing the question of whether the energy of the complex is statistically distributed. Well-escaping trajectories are modeled from these equations, and the escape rate as a function of relative velocity and angular momentum is fitted to an empirical function, which is then integrated over a probability distribution of said quantities. By necessity, this approach makes crude assumptions on the shape of the potential well and neglects the impact of energy quantization, and, more crucially, the coupling between the degrees of freedom included in the equations of motion with those that are not. We quantify the error caused by the first assumption by comparing our model potential with a quantum chemical potential energy surface (PES) and show that while the model does make several compromises and may not be accurate for all classes of bimolecular complexes, it is able to produce physically consistent dissociation rate coefficients within typical atmospheric chemistry confidence intervals for triplet state alkoxyl radical complexes, for which the detailed balance approach has been shown to fail. American Chemical Society 2023-07-07 /pmc/articles/PMC10364079/ /pubmed/37418045 http://dx.doi.org/10.1021/acs.jpca.3c01890 Text en © 2023 The Author. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Franzon, Lauri
Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title_full Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title_fullStr Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title_full_unstemmed Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title_short Simple Physical Model for the Estimation of Irreversible Dissociation Rates for Bimolecular Complexes
title_sort simple physical model for the estimation of irreversible dissociation rates for bimolecular complexes
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10364079/
https://www.ncbi.nlm.nih.gov/pubmed/37418045
http://dx.doi.org/10.1021/acs.jpca.3c01890
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