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Fast Interconversion of Hydrogen Bonding at the Hematite (001)–Liquid Water Interface

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† Department of Physics and Astronomy, University College London, London WC1E 6BT, U.K.
‡ Pacific Northwest National Laboratory, Richland, Washington 99352, United States
*E-mail: [email protected]
*E-mail: [email protected]
Cite this: J. Phys. Chem. Lett. 2016, 7, 7, 1155–1160
Publication Date (Web):March 8, 2016
https://doi.org/10.1021/acs.jpclett.6b00165
Copyright © 2016 American Chemical Society
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Abstract

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The interface between transition-metal oxides and aqueous solutions plays an important role in biogeochemistry and photoelectrochemistry, but the atomistic structure is often elusive. Here we report on the surface geometry, solvation structure, and thermal fluctuations of the hydrogen bonding network at the hematite (001)–water interface as obtained from hybrid density functional theory-based molecular dynamics. We find that the protons terminating the surface form binary patterns by either pointing in-plane or out-of-plane. The patterns exist for about 1 ps and spontaneously interconvert in an ultrafast, solvent-driven process within 50 fs. This results in only about half of the terminating protons pointing toward the solvent and being acidic. The lifetimes of all hydrogen bonds formed at the interface are shorter than those in pure liquid water. The solvation structure reported herein forms the basis for a better fundamental understanding of electron transfer coupled to proton transfer reactions at this important interface.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jpclett.6b00165.

  • Simulation details, coordinates and the HB detection method, the vibrational density of states, two figures showing the Hartree potential across the interface and the surface termination patterns as well as three tables summarizing the HB lifetime distribution and the conditional probabilities for finding a HB alongside the possible angles according to Figure 4 (PDF)

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