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Title: The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF

Abstract

When a solute molecule is placed in solution, is it acceptable to presume that its electronic structure is essentially the same as in the gas phase? In this paper, we address this question from a simulation perspective for the case of the sodium dimer cation (Na2+) molecule in both liquid Ar and liquid tetrahydrofuran (THF). In previous work, we showed that when local specific interactions between a solute and solvent are energetically on the order of a hydrogen bond, the solvent can become part of the chemical identity of the solute. Here, using mixed quantum/classical molecular dynamics simulations, we see that for the Na2+ molecule, solute--solvent interactions lead to two stable, chemically-distinct coordination states (Na(THF)4-Na(THF)5+ and Na(THF)5-Na(THF)5+) that are not only stable themselves as gas-phase molecules but that also have a completely new electronic structure with important implications for the excited-state photodissociation of this molecule in the condensed phase. Furthermore, we show through a set of comparative classical simulations that treating the solute's bonding electron explicitly quantum mechanically is necessary to understand both the ground-state dynamics and chemical identity of this simple diatomic molecule; even use of the quantum-derived potential of mean force is insufficient to describe the behavior ofmore » the molecule classically. Lastly, we calculate the results of a proposed transient hole-burning experiment that could be used to spectroscopically disentangle the presence of the different coordination states.« less

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of California, Los Angeles, CA (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
OSTI Identifier:
1635663
Grant/Contract Number:  
SC0017800
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 124; Journal Issue: 30; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; quantum MD simulation; solvation; chemical identity; chemical bond dynamics

Citation Formats

Widmer, Devon R., and Schwartz, Benjamin J. The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF. United States: N. p., 2020. Web. doi:10.1021/acs.jpcb.0c03298.
Widmer, Devon R., & Schwartz, Benjamin J. The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF. United States. https://doi.org/10.1021/acs.jpcb.0c03298
Widmer, Devon R., and Schwartz, Benjamin J. 2020. "The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF". United States. https://doi.org/10.1021/acs.jpcb.0c03298. https://www.osti.gov/servlets/purl/1635663.
@article{osti_1635663,
title = {The Role of the Solvent in the Condensed-Phase Dynamics and Identity of Chemical Bonds: The Case of the Sodium Dimer Cation in THF},
author = {Widmer, Devon R. and Schwartz, Benjamin J.},
abstractNote = {When a solute molecule is placed in solution, is it acceptable to presume that its electronic structure is essentially the same as in the gas phase? In this paper, we address this question from a simulation perspective for the case of the sodium dimer cation (Na2+) molecule in both liquid Ar and liquid tetrahydrofuran (THF). In previous work, we showed that when local specific interactions between a solute and solvent are energetically on the order of a hydrogen bond, the solvent can become part of the chemical identity of the solute. Here, using mixed quantum/classical molecular dynamics simulations, we see that for the Na2+ molecule, solute--solvent interactions lead to two stable, chemically-distinct coordination states (Na(THF)4-Na(THF)5+ and Na(THF)5-Na(THF)5+) that are not only stable themselves as gas-phase molecules but that also have a completely new electronic structure with important implications for the excited-state photodissociation of this molecule in the condensed phase. Furthermore, we show through a set of comparative classical simulations that treating the solute's bonding electron explicitly quantum mechanically is necessary to understand both the ground-state dynamics and chemical identity of this simple diatomic molecule; even use of the quantum-derived potential of mean force is insufficient to describe the behavior of the molecule classically. Lastly, we calculate the results of a proposed transient hole-burning experiment that could be used to spectroscopically disentangle the presence of the different coordination states.},
doi = {10.1021/acs.jpcb.0c03298},
url = {https://www.osti.gov/biblio/1635663}, journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
number = 30,
volume = 124,
place = {United States},
year = {2020},
month = {6}
}

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