Optical fingerprints of solid-liquid interfaces: a joint ATR-IR and \emph{first principles} investigation

ORAL

Abstract

Despite the importance of understanding the structural and bonding properties of solid-liquid interfaces for a wide range of (photo-)electrochemical applications, there are presently no experimental techniques available to directly probe the microscopic structure of solid-liquid interfaces. To develop robust strategies to interpret experiments and validate theory, we carried out attenuated total internal reflection (ATR-IR) spectroscopy measurements and \emph{ab initio} molecular dynamics (AIMD) simulations of the vibrational properties of interfaces between liquid water and well-controlled prototypical semiconductor substrates. We show the Ge(100)/H$_2$O interface to feature a reversible potential-dependent surface phase transition between Ge-H and Ge-OH termination. The Si(100)/H$_2$O interface is proposed as a model system for corrosion and oxidation processes. We performed AIMD calculations under finite electric fields, revealing different pathways for initial oxidation. These pathways are predicted to exhibit unique spectral signatures. A significant increase in surface specificity can be achieved utilizing an angle-dependent ATR-IR experiment, which allows to detect such signatures at the interfacial layer and consequently changes in the hydrogen bond network.

*Funding from DOE-BES Grant No. DE-SS0008939 and the Deutsche Forschungsgemeinschaft (RESOLV, EXC 1069) are gratefully acknowledged.

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Authors

  • L. Yang

    • Max-Planck-Inst f\"ur Eisenforschung

  • F. Niu

    • Max-Planck-Inst f\"ur Eisenforschung

  • S. Tecklenburg

    • Max-Planck-Inst f\"ur Eisenforschung

  • M. Pander

    • Max-Planck-Inst f\"ur Eisenforschung

  • S. Nayak

    • Max-Planck-Inst f\"ur Eisenforschung

  • A. Erbe

    • Max-Planck-Inst f\"ur Eisenforschung

  • Stefan Wippermann

    • Max Planck Inst fuer Eisenforschung GmbH
    • Max-Planck-Inst f\"ur Eisenforschung

  • Francois Gygi

    • Department of Computer Science, University of California Davis, Davis, CA 95616
    • University of California, Davis, CA 95616, USA
    • University of California, Davis
    • University of California Davis

  • Giulia Galli

    • Univ of Chicago and Argonne National Laboratory
    • Univ of Chicago
    • University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago and Materials Science Division, Argonne Natl Lab
    • Institute for Molecular Engineering, University of Chicago; Materials Science Division, Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago, Chicago, IL 60637 and Materials Science Division, Argonne National Laboratory, Lemont, IL
    • Institute for Molecular Engineering, University of Chicago and Argonne Natl Lab
    • University of Chicago, Chicago, IL 60637, USA
    • The University of Chicago, Institute for Molecular Engineering and Argonne National Laboratory
    • Argonne National Laboratory and University of Chicago
    • Institute for Molecular Engineering, University of Chicago and Materials Science Division, Argonne National Laboratory
    • University of Chicago
    • The University of Chicago
    • University of Chicago and Argonne National Laboratory