Comparison of single-ion molecular dynamics in common solvents

Muralidharan, A.; Pratt, L. R.; Chaudhari, M. I.; Rempe, S. B.

doi:10.1063/1.5023121

Title: Comparison of single-ion molecular dynamics in common solvents

Abstract

Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li⁺ and PF₆^- ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. Here, we provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF₆^-), velocity relaxations are all similar: negative tail relaxations for the VACF and a clear second relaxation for γ(t), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li⁺ ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ(t). But the corresponding analysis of the solventberg Li⁺ (H₂O)₄ does conform to the standard picture set by all the PF₆^- results.

Authors:

Muralidharan, A. ^[1];

^[1]; Chaudhari, M. I. ^[2]; Rempe, S. B. ^[2]

Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Engineering Sciences

Publication Date:: Fri Mar 30 00:00:00 EDT 2018

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1474055

Report Number(s):: SAND-2018-10160J
Journal ID: ISSN 0021-9606; 667921

Grant/Contract Number:: AC04-94AL85000

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 148; Journal Issue: 22; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats


                    Muralidharan, A., Pratt, L. R., Chaudhari, M. I., and Rempe, S. B. Comparison of single-ion molecular dynamics in common solvents.  United States: N. p., 2018. 
Web.  doi:10.1063/1.5023121.

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                    Muralidharan, A., Pratt, L. R., Chaudhari, M. I., & Rempe, S. B. Comparison of single-ion molecular dynamics in common solvents.  United States.  https://doi.org/10.1063/1.5023121

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                    Muralidharan, A., Pratt, L. R., Chaudhari, M. I., and Rempe, S. B. Fri .  
"Comparison of single-ion molecular dynamics in common solvents".  United States.  https://doi.org/10.1063/1.5023121.  https://www.osti.gov/servlets/purl/1474055.

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@article{osti_1474055,

  title        = {Comparison of single-ion molecular dynamics in common solvents},

  author       = {Muralidharan, A. and Pratt, L. R. and Chaudhari, M. I. and Rempe, S. B.},

  abstractNote = {Laying a basis for molecularly specific theory for the mobilities of ions in solutions of practical interest, we report a broad survey of velocity autocorrelation functions (VACFs) of Li+ and PF6- ions in water, ethylene carbonate, propylene carbonate, and acetonitrile solutions. We extract the memory function, γ(t), which characterizes the random forces governing the mobilities of ions. Here, we provide comparisons controlling for the effects of electrolyte concentration and ion-pairing, van der Waals attractive interactions, and solvent molecular characteristics. For the heavier ion (PF6-), velocity relaxations are all similar: negative tail relaxations for the VACF and a clear second relaxation for γ(t), observed previously also for other molecular ions and with n-pentanol as the solvent. For the light Li+ ion, short time-scale oscillatory behavior masks simple, longer time-scale relaxation of γ(t). But the corresponding analysis of the solventberg Li+ (H2O)4 does conform to the standard picture set by all the PF6- results.},

  doi          = {10.1063/1.5023121},

  journal      = {Journal of Chemical Physics},

  number       = 22,

  volume       = 148,

  place        = {United States},

  year         = {Fri Mar 30 00:00:00 EDT 2018},

  month        = {Fri Mar 30 00:00:00 EDT 2018}

}

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Works referencing / citing this record:

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions
journal, February 2018

Chaudhari, Mangesh I.; Muralidharan, Ajay; Pratt, Lawrence R.
Topics in Current Chemistry, Vol. 376, Issue 2
DOI: 10.1007/s41061-018-0187-2

Structures and dynamic properties of the LiPF 6 electrolytic solution under electric fields – a theoretical study
journal, January 2019

Liu, Man; Chimtali, Peter J.; Huang, Xue-bin
Physical Chemistry Chemical Physics, Vol. 21, Issue 24
DOI: 10.1039/c9cp00561g

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Similar Records

Title: Comparison of single-ion molecular dynamics in common solvents

Abstract

Citation Formats

Molecular theory of solvated ion dynamics journal, January 1978

The Hydration Number of Li + in Liquid Water journal, February 2000

A molecular dynamics method for simulations in the canonical ensemble journal, June 1984

Molecular Dynamics Simulation of Li+BF4- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents journal, January 1998

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids journal, January 1996

Algorithm 368: Numerical inversion of Laplace transforms [D5] journal, January 1970

Li + solvation and kinetics of Li + –BF 4 − /PF 6 − ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories journal, October 2017

Molecular Mechanism of Specific Ion Interactions between Alkali Cations and Acetate Anion in Aqueous Solution: A Molecular Dynamics Study journal, June 2012

Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids journal, June 1971

Analysis of the velocity autocorrelation function of water journal, August 1996

Generalized Langevin theory for many‐body problems in chemical dynamics: Reactions in liquids journal, October 1980

Computational studies of water exchange around aqueous Li + with polarizable potential models journal, August 2013

Generalizations of the Fuoss approximation for ion pairing journal, February 2011

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion journal, November 2016

Polymorphic transitions in single crystals: A new molecular dynamics method journal, December 1981

Understanding the Rates and Molecular Mechanism of Water-Exchange around Aqueous Ions Using Molecular Simulations journal, June 2014

Effect of water on structure and dynamics of [BMIM][PF 6 ] ionic liquid: An all-atom molecular dynamics simulation investigation journal, March 2016

Longitudinal modes, transverse modes and velocity correlations in liquids. I journal, September 1978

Pairing of 1-hexyl-3-methylimidazolium and tetrafluoroborate ions in n -pentanol journal, November 2012

The missing term in effective pair potentials journal, November 1987

Neutron Scattering Studies of the Hydration Structure of Li + journal, January 2015

Computing the 7Li NMR chemical shielding of hydrated Li+ using cluster calculations and time-averaged configurations from ab initio molecular dynamics simulations journal, January 2011

A molecular dynamics method for simulations in the canonical ensemble journal, January 2002

Generalizations of the Fuoss Approximation for Ion Pairing text, January 2010

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions journal, February 2018

Structures and dynamic properties of the LiPF 6 electrolytic solution under electric fields – a theoretical study journal, January 2019

Molecular theory of solvated ion dynamics
journal, January 1978

The Hydration Number of Li ⁺ in Liquid Water
journal, February 2000

A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984

Molecular Dynamics Simulation of Li⁺BF₄^- in Ethylene Carbonate, Propylene Carbonate, and Dimethyl Carbonate Solvents
journal, January 1998

Development and Testing of the OPLS All-Atom Force Field on Conformational Energetics and Properties of Organic Liquids
journal, January 1996

Algorithm 368: Numerical inversion of Laplace transforms [D5]
journal, January 1970

Li ⁺ solvation and kinetics of Li ⁺ –BF ₄ ⁻ /PF ₆ ⁻ ion pairs in ethylene carbonate. A molecular dynamics study with classical rate theories
journal, October 2017

Molecular Mechanism of Specific Ion Interactions between Alkali Cations and Acetate Anion in Aqueous Solution: A Molecular Dynamics Study
journal, June 2012

Role of Repulsive Forces in Determining the Equilibrium Structure of Simple Liquids
journal, June 1971

Analysis of the velocity autocorrelation function of water
journal, August 1996

Generalized Langevin theory for many‐body problems in chemical dynamics: Reactions in liquids
journal, October 1980

Computational studies of water exchange around aqueous Li ⁺ with polarizable potential models
journal, August 2013

Generalizations of the Fuoss approximation for ion pairing
journal, February 2011

Scaling Atomic Partial Charges of Carbonate Solvents for Lithium Ion Solvation and Diffusion
journal, November 2016

Polymorphic transitions in single crystals: A new molecular dynamics method
journal, December 1981

Understanding the Rates and Molecular Mechanism of Water-Exchange around Aqueous Ions Using Molecular Simulations
journal, June 2014

Effect of water on structure and dynamics of [BMIM][PF ₆ ] ionic liquid: An all-atom molecular dynamics simulation investigation
journal, March 2016

Longitudinal modes, transverse modes and velocity correlations in liquids. I
journal, September 1978

Pairing of 1-hexyl-3-methylimidazolium and tetrafluoroborate ions in n -pentanol
journal, November 2012

The missing term in effective pair potentials
journal, November 1987

Neutron Scattering Studies of the Hydration Structure of Li ⁺
journal, January 2015

Computing the 7Li NMR chemical shielding of hydrated Li+ using cluster calculations and time-averaged configurations from ab initio molecular dynamics simulations
journal, January 2011

A molecular dynamics method for simulations in the canonical ensemble
journal, January 2002

Generalizations of the Fuoss Approximation for Ion Pairing
text, January 2010

Assessment of Simple Models for Molecular Simulation of Ethylene Carbonate and Propylene Carbonate as Solvents for Electrolyte Solutions
journal, February 2018

Structures and dynamic properties of the LiPF 6 electrolytic solution under electric fields – a theoretical study
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