Three-Body Hydrogen Bond Defects Contribute Significantly to the Dielectric Properties of the Liquid Water–Vapor Interface
Name
1710.04267.pdf
Description
Submitted version
Size
1.49 MB
Format
Adobe PDF
Checksum (MD5)
248d898ca5f37b35bdcd15dbd2397cca
Author(s)
Shin, Sucheol
Willard, Adam P.
Date Issued
March 2018
Journal
The journal of physical chemistry letters
Publisher
American Chemical Society (ACS)
Citation
Shin, Sucheol and Adam P. Willard. “Three-Body Hydrogen Bond Defects Contribute Significantly to the Dielectric Properties of the Liquid Water–Vapor Interface.” The journal of physical chemistry letters 9 (2018): 1649-1654.
Version
Original manuscript
Abstract
We present a simple model of aqueous interfacial molecular structure, and we use this model to isolate the effects of hydrogen bonding on the dielectric properties of the liquid water-vapor interface. We show that water's interfacial molecular structure can be understood by considering the orientational preferences of a single molecule immersed in the environment of the average interfacial density field. We illustrate that depth-dependent orientational anisotropy is determined by the geometric constraints of hydrogen bonding, and we show that the primary features of atomistic simulation data can be reproduced by assuming an idealized, perfectly tetrahedral hydrogen bonding geometry. We demonstrate that nonideal hydrogen bond geometries are required to account for variations in the orientational polarization and polarizability of the interface. Finally, we highlight that these properties contain significant contributions from a specific type of geometrically distorted three-body hydrogen bond defect that is preferentially stabilized at the interface.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1021/ACS.JPCLETT.8B00488
