The Importance of the Water Molecular Quadrupole for Estimating Interfacial Potential Shifts Acting on Ions Near the Liquid-Vapor Interface

Carrie C. Doyle; Yu Shi; Thomas L. Beck

doi:10.1021/acs.jpcb.9b01289

The Importance of the Water Molecular Quadrupole for Estimating Interfacial Potential Shifts Acting on Ions Near the Liquid-Vapor Interface

Carrie C. Doyle, Yu Shi, Thomas L. Beck

Research output: Contribution to journal › Article › peer-review

30 Scopus citations

Abstract

Interfacial electrostatic potential gradients arise from nonuniform charge distributions encountered crossing the interface. The charges involved can include the molecular charges predominantly bound to each neutral solvent molecule and distributions of ions (or electrons) free to move in the interfacial region. This paper focuses on the solvent contribution to the interfacial potential. Quasichemical theory (QCT) provides a physical framework for the analysis of near-local (chemical) and far-field contributions to ion solvation free energies. Here, we utilize QCT to analyze cavity net potentials that contribute to the single-ion real solvation free energy. In particular, we discuss the results of molecular dynamics simulations of water droplets large enough to exhibit bulklike behavior in the droplet interior. A multipolar analysis of the cavity potential illustrates the importance of the solvent molecular quadrupole due to the near-cancellation of the dipolar contributions from the cavity-liquid and liquid-vapor interfaces. The results reveal the physical origin of the previously observed strong classical model dependence of the cavity potential.

Original language	English
Pages (from-to)	3348-3358
Number of pages	11
Journal	Journal of Physical Chemistry B
Volume	123
Issue number	15
DOIs	https://doi.org/10.1021/acs.jpcb.9b01289
State	Published - Apr 18 2019
Externally published	Yes

Funding

We gratefully acknowledge the financial support of the National Science Foundation (grant CHE-1565632) and a generous grant of computing resources from the Ohio Supercomputer Center. We also thank the College of Arts and Sciences in the University of Cincinnati for postdoctoral support for Y.S. We thank Travis Pollard, Lawrence Pratt, Barry Ninham, Pierandrea Lo Nostro, John Palmeri, Toshiko Ichiye, Chris Mundy, Greg Schenter, Shawn Kathmann, Tim Duignan, and Marcel Baer for helpful and informative discussions.

Funders	Funder number
National Science Foundation	CHE-1565632

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10.1021/acs.jpcb.9b01289

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title = "The Importance of the Water Molecular Quadrupole for Estimating Interfacial Potential Shifts Acting on Ions Near the Liquid-Vapor Interface",

abstract = "Interfacial electrostatic potential gradients arise from nonuniform charge distributions encountered crossing the interface. The charges involved can include the molecular charges predominantly bound to each neutral solvent molecule and distributions of ions (or electrons) free to move in the interfacial region. This paper focuses on the solvent contribution to the interfacial potential. Quasichemical theory (QCT) provides a physical framework for the analysis of near-local (chemical) and far-field contributions to ion solvation free energies. Here, we utilize QCT to analyze cavity net potentials that contribute to the single-ion real solvation free energy. In particular, we discuss the results of molecular dynamics simulations of water droplets large enough to exhibit bulklike behavior in the droplet interior. A multipolar analysis of the cavity potential illustrates the importance of the solvent molecular quadrupole due to the near-cancellation of the dipolar contributions from the cavity-liquid and liquid-vapor interfaces. The results reveal the physical origin of the previously observed strong classical model dependence of the cavity potential.",

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AB - Interfacial electrostatic potential gradients arise from nonuniform charge distributions encountered crossing the interface. The charges involved can include the molecular charges predominantly bound to each neutral solvent molecule and distributions of ions (or electrons) free to move in the interfacial region. This paper focuses on the solvent contribution to the interfacial potential. Quasichemical theory (QCT) provides a physical framework for the analysis of near-local (chemical) and far-field contributions to ion solvation free energies. Here, we utilize QCT to analyze cavity net potentials that contribute to the single-ion real solvation free energy. In particular, we discuss the results of molecular dynamics simulations of water droplets large enough to exhibit bulklike behavior in the droplet interior. A multipolar analysis of the cavity potential illustrates the importance of the solvent molecular quadrupole due to the near-cancellation of the dipolar contributions from the cavity-liquid and liquid-vapor interfaces. The results reveal the physical origin of the previously observed strong classical model dependence of the cavity potential.

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The Importance of the Water Molecular Quadrupole for Estimating Interfacial Potential Shifts Acting on Ions Near the Liquid-Vapor Interface

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