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Title: Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

Abstract

The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

Authors:
;  [1]
  1. Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70808 (United States)
Publication Date:
OSTI Identifier:
22493469
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 143; Journal Issue: 4; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BOND LENGTHS; CHEMICAL BONDS; COMPUTERIZED TOMOGRAPHY; HYDROGEN; HYDROXIDES; INTERFACES; IONS; LIQUIDS; MOLECULES; PROTONS; SURFACE WATERS; SURFACES; VALENCE; VAPORS; WATER

Citation Formats

Soniat, Marielle, Rick, Steven W., E-mail: srick@uno.edu, and Kumar, Revati. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water. United States: N. p., 2015. Web. doi:10.1063/1.4926831.
Soniat, Marielle, Rick, Steven W., E-mail: srick@uno.edu, & Kumar, Revati. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water. United States. https://doi.org/10.1063/1.4926831
Soniat, Marielle, Rick, Steven W., E-mail: srick@uno.edu, and Kumar, Revati. 2015. "Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water". United States. https://doi.org/10.1063/1.4926831.
@article{osti_22493469,
title = {Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water},
author = {Soniat, Marielle and Rick, Steven W., E-mail: srick@uno.edu and Kumar, Revati},
abstractNote = {The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.},
doi = {10.1063/1.4926831},
url = {https://www.osti.gov/biblio/22493469}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 143,
place = {United States},
year = {Tue Jul 28 00:00:00 EDT 2015},
month = {Tue Jul 28 00:00:00 EDT 2015}
}