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Title: Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity

Abstract

In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $$^+_2$$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $$^+_2$$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $$^+_2$$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. University of California, Los Angeles, LA (United States)
Publication Date:
Research Org.:
Univ. of California, Los Angeles, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1673161
Grant/Contract Number:  
SC0017800; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 21; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Photodissociation; quantum simulation; condensed-phase; energy release

Citation Formats

Vong, Andy, Widmer, Devon R., and Schwartz, Benjamin J. Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity. United States: N. p., 2020. Web. doi:10.1021/acs.jpclett.0c02515.
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Vong, Andy, Widmer, Devon R., & Schwartz, Benjamin J. Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity. United States. https://doi.org/10.1021/acs.jpclett.0c02515
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Vong, Andy, Widmer, Devon R., and Schwartz, Benjamin J. Fri . "Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity". United States. https://doi.org/10.1021/acs.jpclett.0c02515. https://www.osti.gov/servlets/purl/1673161.
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@article{osti_1673161,
title = {Nonequilibrium Solvent Effects during Photodissociation in Liquids: Dynamical Energy Surfaces, Caging and Chemical Identity},
author = {Vong, Andy and Widmer, Devon R. and Schwartz, Benjamin J.},
abstractNote = {In the gas phase, potential energy surfaces can be used to provide insight into the details of photochemical reaction dynamics. In solution, however, it is unclear what potential energy surfaces, if any, can be used to describe even simple chemical reactions such as the photodissociation of a diatomic solute. In this paper, we use mixed quantum/classical (MQC) molecular dynamics (MD) to study the photodissociation of $Na$ $^+_2$ in both liquid Ar and liquid tetrahydrofuran (THF). We examine both the gas-phase potential surfaces and potentials of mean force (PMF), which assume that the solvent remains at equilibrium with the solute throughout the photodissociation process and show that neither resemble a nonequilibrium dynamical energy surface that is generated by taking the time integral of work. For the photodissociation of $Na$ $^+_2$ in liquid Ar, the dynamical energy surface shows clear signatures of solvent caging, and the degree of caging is directly related to the mass of the solvent atoms. For $Na$ $^+_2$ in liquid THF, local specific interactions between the solute and solvent lead to changes in chemical identity that create a kinetic trap that effectively prevents the molecule from dissociating. Here, the results show that nonequilibrium effects play an important role even in simple solution-phase reactions, requiring the use of dynamical energy surface to understand such chemical events.},
doi = {10.1021/acs.jpclett.0c02515},
journal = {Journal of Physical Chemistry Letters},
number = 21,
volume = 11,
place = {United States},
year = {Fri Oct 16 00:00:00 EDT 2020},
month = {Fri Oct 16 00:00:00 EDT 2020}
}
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