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

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

Full Record
Other Related Research

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 (Na ₂ ⁺) 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 Na ₂ ⁺ 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 potentialmore »« 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 Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry; 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.

Copy to clipboard


                    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.  doi:10.1021/acs.jpcb.0c03298.

Copy to clipboard


                    Widmer, Devon R., and Schwartz, Benjamin J. Tue .  
        "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.  doi:10.1021/acs.jpcb.0c03298.

Copy to clipboard


                    
@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},

  journal      = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},

  issn         = {1520-6106},

  number       = ,

  volume       = ,

  place        = {United States},

  year         = {2020},

  month        = {6}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

This content will become publicly available on June 30, 2021

Publisher's Version of Record

DOI: 10.1021/acs.jpcb.0c03298

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar records in OSTI.GOV collections:

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

Journal Article Vong, Andy ; Widmer, Devon R. ; Schwartz, Benjamin J. - Journal of Physical Chemistry Letters

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 ofmore »« less
DOI: 10.1021/acs.jpclett.0c02515
Solvents can control solute molecular identity

Journal Article Widmer, Devon. R. ; Schwartz, Benjamin J. - Nature Chemistry

For solution-phase chemical reactions, the solvent is often considered simply as a medium to allow the reactants to encounter each other by diffusion. Although examples of direct solvent effects on molecular solutes exist, such as the compression of solute bonding electrons due to Pauli repulsion interactions, the solvent is not usually considered a part of the chemical species of interest. We show, using quantum simulations of Na ₂, that when there are local specific interactions between a solute and solvent that are energetically on the same order as a hydrogen bond, the solvent controls not only the bond dynamics butmore »« less
Cited by 6
DOI: 10.1038/s41557-018-0066-z

Full Text Available
Preparation and characterization of NaW/sub 2/Cl/sub 7/(THF)/sub 5/. A Synthetically useful precursor for X/sub 3/W identical with WX/sub 3/ compounds where X = CH/sub 2/-t-Bu, NMe/sub 2/, and O-t-Bu

Journal Article Chisholm, M H ; Eichhorn, B W ; Folting, K ; ... - Inorg. Chem.; (United States)

From the addition of Na/Hg (1 equiv) to a WCl/sub 4/ slurry in THF (THF = tetrahydrofuran) was obtained the green crystalline compound NaW/sub 2/Cl/sub 7/(THF)/sub 5/ in 60-70% recrystallized yields. The compound has been shown to involve a confacial bioctahedral W/sub 2/Cl/sub 7/(THF)/sub 2//sup -/ anion coordinated to a (THF)/sub 3/Na/sup +/ cation via two chloride ligands that are terminally bonded to W atoms. The W-W distance 2.4028 (15) A is essentially identical with that seen in other W/sub 2/X/sub 9//sup 3 -/ anions (X = Cl or Br) and is indicative of strong t/sub 2g//sup 3/-t/sub 2g//sup 3/more »« less
DOI: 10.1021/ic00266a024
Moving solvated electrons with light: Nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF)

Journal Article Bedard-Hearn, Michael J ; Larsen, Ross E ; Schwartz, Benjamin J - Journal of Chemical Physics

Motivated by recent ultrafast spectroscopic experiments [Martini et al., Science 293, 462 (2001)], which suggest that photoexcited solvated electrons in tetrahydrofuran (THF) can relocalize (that is, return to equilibrium in solvent cavities far from where they started), we performed a series of nonequilibrium, nonadiabatic, mixed quantum/classical molecular dynamics simulations that mimic one-photon excitation of the THF-solvated electron. We find that as photoexcited THF-solvated electrons relax to their ground states either by continuous mixing from the excited state or via nonadiabatic transitions, {approx}30% of them relocalize into cavities that can be over 1 nm away from where they originated, in closemore »« less
DOI: 10.1063/1.2358131
Elucidating the structure of the magnesium aluminum chloride complex electrolyte for magnesium-ion batteries

Journal Article Canepa, Pieremanuele ; Jayaraman, Saivenkataraman ; Cheng, Lei ; ... - Energy & Environmental Science

Non-aqueous Mg-ion batteries offer a promising way to overcome safety, costs, and energy density limitations of state-of-the-art Li-ion battery technology. Here, we present a rigorous analysis of the magnesium aluminum chloride complex (MACC) in tetrahydrofuran (THF), one of the few electrolytes that can reversibly plate and strip Mg. We use ab initio calculations and classical molecular dynamics simulations to interrogate the MACC electrolyte composition with the goal of addressing two urgent questions that have puzzled battery researchers: (i) the functional species of the electrolyte, and (ii) the complex equilibria regulating the MACC speciation after prolonged electrochemical cycling, a process termedmore »« less
Cited by 53
DOI: 10.1039/c5ee02340h

Full Text Available

Similar Records