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

Widmer, Devon R.; Schwartz, Benjamin J.

doi:10.1021/acs.jpcb.0c03298

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 »« less

Authors:

Widmer, Devon R. ^[1];

^[1]

Univ. of California, Los Angeles, CA (United States)

Publication Date:: 2020-06-30

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.

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                    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

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                    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.

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@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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Similar Records

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

Citation Formats

Solvents can control solute molecular identity journal, May 2018

Dynamics of Solvated Electrons in Clusters journal, June 2012

Theory and applications of charge-transfer-to-solvent spectra journal, February 1970

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I journal, May 1956

Electron transfers in chemistry and biology journal, August 1985

How Does the Solvent Control Electron Transfer? Experimental and Theoretical Studies of the Simplest Charge Transfer Reaction journal, December 2001

The Nature of Simple Photodissociation Reactions in Liquids on Ultrafast Time Scales journal, October 1988

How Does a Solvent Affect Chemical Bonds? Mixed Quantum/Classical Simulations with a Full CI Treatment of the Bonding Electrons journal, November 2009

Pulse radiolysis studies. XXII. Spectrum and kinetics of the sodium cation-electron pair in tetrahydrofuran solutions journal, April 1973

Observation of above-threshold dissociation of Na 2 + in intense laser fields journal, August 2008

Detailed experimental and theoretical study of collision-induced dissociation of Na 2 + ions on He and H 2 targets at keV energies journal, February 1998

Analysis of Collision Induced Dissociation of Na 2 + Molecular Ions journal, August 1996

Model potential calculations for the ground, excited and Rydberg 2Σ states of Li2+, Na2+ and K2+: Core polarization effects journal, November 1983

The electronic structure of some diatomic molecules journal, January 1929

Representation of simple molecules by molecular orbitals journal, January 1947

New Method for Calculating Wave Functions in Crystals and Molecules journal, October 1959

A computationally efficient exact pseudopotential method. I. Analytic reformulation of the Phillips-Kleinman theory journal, August 2006

A computationally efficient exact pseudopotential method. II. Application to the molecular pseudopotential of an excess electron interacting with tetrahydrofuran (THF) journal, August 2006

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

The nature of dilute solutions of sodium ion in water, methanol, and tetrahydrofuran journal, November 1982

Nature of Sodium Atoms/(Na + , e − ) Contact Pairs in Liquid Tetrahydrofuran journal, September 2010

Reaction field simulation of water journal, February 1982

The interatomic potential for the X1Σ+ state of ArNa+, NeNa+ and HeNa+ journal, October 1995

Phase diagrams of Lennard‐Jones fluids journal, June 1992

Solvents can control solute molecular identity
journal, May 2018

Dynamics of Solvated Electrons in Clusters
journal, June 2012

Theory and applications of charge-transfer-to-solvent spectra
journal, February 1970

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956

Electron transfers in chemistry and biology
journal, August 1985

How Does the Solvent Control Electron Transfer? Experimental and Theoretical Studies of the Simplest Charge Transfer Reaction
journal, December 2001

The Nature of Simple Photodissociation Reactions in Liquids on Ultrafast Time Scales
journal, October 1988

How Does a Solvent Affect Chemical Bonds? Mixed Quantum/Classical Simulations with a Full CI Treatment of the Bonding Electrons
journal, November 2009

Pulse radiolysis studies. XXII. Spectrum and kinetics of the sodium cation-electron pair in tetrahydrofuran solutions
journal, April 1973

Observation of above-threshold dissociation of ${Na}_{2}^{+}$ in intense laser fields
journal, August 2008

Detailed experimental and theoretical study of collision-induced dissociation of ${Na}_{2}^{+}$ ions on He and $H_{2}$ targets at keV energies
journal, February 1998

Analysis of Collision Induced Dissociation of ${Na}_{2}^{+}$ Molecular Ions
journal, August 1996

Model potential calculations for the ground, excited and Rydberg 2Σ states of Li2+, Na2+ and K2+: Core polarization effects
journal, November 1983

The electronic structure of some diatomic molecules
journal, January 1929

Representation of simple molecules by molecular orbitals
journal, January 1947

New Method for Calculating Wave Functions in Crystals and Molecules
journal, October 1959

A computationally efficient exact pseudopotential method. I. Analytic reformulation of the Phillips-Kleinman theory
journal, August 2006

A computationally efficient exact pseudopotential method. II. Application to the molecular pseudopotential of an excess electron interacting with tetrahydrofuran (THF)
journal, August 2006

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

The nature of dilute solutions of sodium ion in water, methanol, and tetrahydrofuran
journal, November 1982

Nature of Sodium Atoms/(Na ⁺ , e ⁻ ) Contact Pairs in Liquid Tetrahydrofuran
journal, September 2010

Reaction field simulation of water
journal, February 1982

The interatomic potential for the X1Σ+ state of ArNa+, NeNa+ and HeNa+
journal, October 1995

Phase diagrams of Lennard‐Jones fluids
journal, June 1992