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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:
 [1]; ORCiD logo [1];  [2];  [2]
  1. Tulane Univ., New Orleans, LA (United States). Dept. of Chemical and Biomolecular Engineering
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Center for Biological and Engineering Sciences
Publication Date:
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.
Muralidharan, A., Pratt, L. R., Chaudhari, M. I., & Rempe, S. B. Comparison of single-ion molecular dynamics in common solvents. United States. doi:10.1063/1.5023121.
Muralidharan, A., Pratt, L. R., Chaudhari, M. I., and Rempe, S. B. Fri . "Comparison of single-ion molecular dynamics in common solvents". United States. doi:10.1063/1.5023121. https://www.osti.gov/servlets/purl/1474055.
@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 = {2018},
month = {3}
}

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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

    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