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Title: Alumina(0001)/Water Interface: Structural Properties and Infrared Spectra from First-Principles Molecular Dynamics Simulations

Journal Article · · Journal of Physical Chemistry. C
DOI:https://doi.org/10.1021/jp4123002· OSTI ID:1798023
 [1];  [2];  [3];  [1]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of California, Davis, CA (United States)
  3. Univ. of Chicago, IL (United States)
+ Show Author Affiliations

We investigated the atomic structure and infrared spectra of the alumina(0001)/water interface, using first-principles molecular dynamics simulations based on density functional theory within the generalized gradient approximation. The computed structural properties of the interface are in good agreement with the results of synchrotron X-ray experiments. In this work detailed analyses of the computed infrared spectra revealed two types of water molecules at the hydrophilic oxide/water interface: molecules participating in strong “ice-like” hydrogen bonding with the oxide surface and molecules involved in weaker “liquid-like” hydrogen bonding. Our results provide a molecular interpretation of the “ice-like” and “liquid-like” bands observed in sum-frequency vibrational spectroscopy experiments and underscore the significance of strong hydrogen-bonding interactions in determining the orientation of interfacial water molecules.

Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC52-07NA27344; SC0008938
OSTI ID:
1798023
Report Number(s):
LLNL-JRNL-641751; 760528
Journal Information:
Journal of Physical Chemistry. C, Vol. 118, Issue 17; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

First Principles Estimation of Geochemically Important Transition Metal Oxide Properties book June 2016
Ab initio simulations of liquid electrolytes for energy conversion and storage journal October 2018
Modelling heterogeneous interfaces for solar water splitting journal January 2017
Enhancing water permeation through alumina membranes by changing from cylindrical to conical nanopores journal January 2019
Vibrational spectroscopy of hydroxylated α-Al 2 O 3 (0001) surfaces with and without water: An ab initio molecular dynamics study journal July 2018
Vibrational spectra of dissociatively adsorbed D 2 O on Al-terminated α-Al 2 O 3 (0001) surfaces from ab initio molecular dynamics journal June 2019
Can Ice-Like Structures Form on Non-Ice-Like Substrates? The Example of the K-feldspar Microcline journal March 2016

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Infrared light
Interfaces
Noncovalent interactions
Layers
Molecules