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 »
- Authors:
-
- 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}
}
Works referenced in this record:
Solvents can control solute molecular identity
journal, May 2018
- Widmer, Devon. R.; Schwartz, Benjamin J.
- Nature Chemistry, Vol. 10, Issue 9
Dynamics of Solvated Electrons in Clusters
journal, June 2012
- Young, Ryan M.; Neumark, Daniel M.
- Chemical Reviews, Vol. 112, Issue 11
Theory and applications of charge-transfer-to-solvent spectra
journal, February 1970
- Blandamer, Michael J.; Fox, Malcom F.
- Chemical Reviews, Vol. 70, Issue 1
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956
- Marcus, R. A.
- The Journal of Chemical Physics, Vol. 24, Issue 5
Electron transfers in chemistry and biology
journal, August 1985
- Marcus, R. A.; Sutin, Norman
- Biochimica et Biophysica Acta (BBA) - Reviews on Bioenergetics, Vol. 811, Issue 3
How Does the Solvent Control Electron Transfer? Experimental and Theoretical Studies of the Simplest Charge Transfer Reaction
journal, December 2001
- Barthel, Erik R.; Martini, Ignacio B.; Schwartz, Benjamin J.
- The Journal of Physical Chemistry B, Vol. 105, Issue 49
The Nature of Simple Photodissociation Reactions in Liquids on Ultrafast Time Scales
journal, October 1988
- Harris, A. L.; Brown, J. K.; Harris, C. B.
- Annual Review of Physical Chemistry, Vol. 39, Issue 1
How Does a Solvent Affect Chemical Bonds? Mixed Quantum/Classical Simulations with a Full CI Treatment of the Bonding Electrons
journal, November 2009
- Glover, William J.; Larsen, Ross E.; Schwartz, Benjamin J.
- The Journal of Physical Chemistry Letters, Vol. 1, Issue 1
Pulse radiolysis studies. XXII. Spectrum and kinetics of the sodium cation-electron pair in tetrahydrofuran solutions
journal, April 1973
- Bockrath, Bradley; Dorfman, Leon M.
- The Journal of Physical Chemistry, Vol. 77, Issue 8
Observation of above-threshold dissociation of in intense laser fields
journal, August 2008
- Zhang, Qun; Hepburn, John W.; Shapiro, Moshe
- Physical Review A, Vol. 78, Issue 2
Detailed experimental and theoretical study of collision-induced dissociation of ions on He and targets at keV energies
journal, February 1998
- Fayeton, J. A.; Barat, M.; Brenot, J. C.
- Physical Review A, Vol. 57, Issue 2
Analysis of Collision Induced Dissociation of Molecular Ions
journal, August 1996
- Brenot, J. C.; Dunet, H.; Fayeton, J. A.
- Physical Review Letters, Vol. 77, Issue 7
Model potential calculations for the ground, excited and Rydberg 2Σ states of Li2+, Na2+ and K2+: Core polarization effects
journal, November 1983
- Henriet, A.; Masnou-Seeuws, F.
- Chemical Physics Letters, Vol. 101, Issue 6
The electronic structure of some diatomic molecules
journal, January 1929
- Lennard-Jones, J. E.
- Transactions of the Faraday Society, Vol. 25
Representation of simple molecules by molecular orbitals
journal, January 1947
- Coulson, C. A.
- Quarterly Reviews, Chemical Society, Vol. 1, Issue 2
New Method for Calculating Wave Functions in Crystals and Molecules
journal, October 1959
- Phillips, James C.; Kleinman, Leonard
- Physical Review, Vol. 116, Issue 2
A computationally efficient exact pseudopotential method. I. Analytic reformulation of the Phillips-Kleinman theory
journal, August 2006
- Smallwood, C. Jay; Larsen, Ross E.; Glover, William J.
- The Journal of Chemical Physics, Vol. 125, Issue 7
A computationally efficient exact pseudopotential method. II. Application to the molecular pseudopotential of an excess electron interacting with tetrahydrofuran (THF)
journal, August 2006
- Smallwood, C. Jay; Mejia, Cesar N.; Glover, William J.
- The Journal of Chemical Physics, Vol. 125, Issue 7
The roles of electronic exchange and correlation in charge-transfer-to-solvent dynamics: Many-electron nonadiabatic mixed quantum/classical simulations of photoexcited sodium anions in the condensed phase
journal, October 2008
- Glover, William J.; Larsen, Ross E.; Schwartz, Benjamin J.
- The Journal of Chemical Physics, Vol. 129, Issue 16
The nature of dilute solutions of sodium ion in water, methanol, and tetrahydrofuran
journal, November 1982
- Chandrasekhar, Jayaraman; Jorgensen, William L.
- The Journal of Chemical Physics, Vol. 77, Issue 10
Nature of Sodium Atoms/(Na + , e − ) Contact Pairs in Liquid Tetrahydrofuran
journal, September 2010
- Glover, William J.; Larsen, Ross E.; Schwartz, Benjamin J.
- The Journal of Physical Chemistry B, Vol. 114, Issue 35
Reaction field simulation of water
journal, February 1982
- Steinhauser, O.
- Molecular Physics, Vol. 45, Issue 2
The interatomic potential for the X1Σ+ state of ArNa+, NeNa+ and HeNa+
journal, October 1995
- Reza Ahmadi, G.; Almlöf, J.; Røeggen, I.
- Chemical Physics, Vol. 199, Issue 1
Phase diagrams of Lennard‐Jones fluids
journal, June 1992
- Smit, B.
- The Journal of Chemical Physics, Vol. 96, Issue 11