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Title: Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement

Abstract

We report that solvent density fluctuations play a crucial role in liquid-vapor transitions in solvophobic confinement and can also be important for understanding solvation of polar and apolar solutes. In the case of ionic liquids (ILs), density fluctuations can be used to understand important processes in the context of nanoscale aggregation and colloidal self-assemblies. In this article, we explore the nature of density fluctuations associated with capillary evaporation of the IL 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) in the confined region of model solvophobic nanoscale sheets by using molecular dynamics simulations combined with non-Boltzmann sampling techniques. We demonstrate that density fluctuations of the confined IL play an important role in capillary evaporation, suggesting analogies to dewetting transitions involving water. Lastly, significant changes in the interfacial structure of the IL are also detailed and suggested to underlie a non-classical (non-parabolic) dependence of the free energy barrier to evaporation on the degree of confinement.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
+ Show Author Affiliations
  1. Indian Institute of Technology Delhi, Hauz Khas, New Delhi (India)
  2. Temple University, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for the Computational Design of Functional Layered Materials (CCDM)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1470140
Alternate Identifier(s):
OSTI ID: 1418409
Grant/Contract Number:  
SC0012575
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 19; Related Information: CCDM partners with Temple University (lead); Brookhaven National Laboratory; Drexel University; Duke University; North Carolina State University; Northeastern University; Princeton University; Rice University; University of Pennsylvania; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); solar (photovoltaic); energy storage (including batteries and capacitors); hydrogen and fuel cells; defects; mechanical behavior; materials and chemistry by design; synthesis (novel materials)

Citation Formats

Shrivastav, Gourav, Remsing, Richard C., and Kashyap, Hemant K.. Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement. United States: N. p., 2018. Web. doi:10.1063/1.5010259.
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Shrivastav, Gourav, Remsing, Richard C., & Kashyap, Hemant K.. Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement. United States. https://doi.org/10.1063/1.5010259
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Shrivastav, Gourav, Remsing, Richard C., and Kashyap, Hemant K.. Mon . "Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement". United States. https://doi.org/10.1063/1.5010259. https://www.osti.gov/servlets/purl/1470140.
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@article{osti_1470140,
title = {Capillary evaporation of the ionic liquid [EMIM][BF4] in nanoscale solvophobic confinement},
author = {Shrivastav, Gourav and Remsing, Richard C. and Kashyap, Hemant K.},
abstractNote = {We report that solvent density fluctuations play a crucial role in liquid-vapor transitions in solvophobic confinement and can also be important for understanding solvation of polar and apolar solutes. In the case of ionic liquids (ILs), density fluctuations can be used to understand important processes in the context of nanoscale aggregation and colloidal self-assemblies. In this article, we explore the nature of density fluctuations associated with capillary evaporation of the IL 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) in the confined region of model solvophobic nanoscale sheets by using molecular dynamics simulations combined with non-Boltzmann sampling techniques. We demonstrate that density fluctuations of the confined IL play an important role in capillary evaporation, suggesting analogies to dewetting transitions involving water. Lastly, significant changes in the interfacial structure of the IL are also detailed and suggested to underlie a non-classical (non-parabolic) dependence of the free energy barrier to evaporation on the degree of confinement.},
doi = {10.1063/1.5010259},
journal = {Journal of Chemical Physics},
number = 19,
volume = 148,
place = {United States},
year = {2018},
month = {1}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1063/1.5010259
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Cited by: 13 works
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Figures / Tables:

FIG. 1 FIG. 1: Representative simulation snapshots for the (a) liquid and (b) vapor phase in the confinement of nanoscale solvophobic square sheets. (c) Structure of [EMIM][BF4] used in the study. Only heavy atoms are shown for clarity.
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text, January 2013

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    Works referencing / citing this record:

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