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The Structure of Benzoquinone Chemisorbed on Pd(111): Simulation of EC-STM Images and HREELS Spectra by Density Functional Theory

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Abstract

Earlier studies on the chemisorption of hydroquinone (H2Q) on well-defined Pd(111) surfaces based on electrochemistry, high-resolution electron energy loss spectroscopy, and in situ scanning tunneling microscopy revealed that H2Q undergoes oxidative chemisorption to generate an adlayer of benzoquinone oriented flat, albeit with a slight tilt. Certain structural details, however, such as the actual adsorbate structure and the surface coordination site could not be unambiguously confirmed solely from the experimental measurements. Density functional theory was thus employed not only to calculate the total adsorption energies of the likely configurations but also to simulate their respective vibrational spectra. The results suggest that: (1) the flat-adsorbed quinone ring is centered on a bridge site in which the C2 axis that points along the para-oxygen atoms is rotated 30° from the [110] direction of the Pd(111) substrate; (2) the p-oxygen atoms are located above twofold sites; and (3) quinonoid ring is slightly puckered with the C–H bonds tilted away from the surface, at an angle of approximately 20°.

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Acknowledgments

Acknowledgment is made to the Texas A&M University-CONACYT Collaborative Research Grant Program for partial financial support, to the Center for Electrochemical Systems and Hydrogen Research for equipment use, and to the Laboratory for Molecular Simulation (Dr. L. M. Perez) at Texas A&M University for the computational software and computer time.

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Authors and Affiliations

  1. Department of Chemistry, Texas A&M University, College Station, TX, 77843, USA

    Alnald Javier, Youn-Geun Kim, Jack Hess Baricuatro & Manuel P. Soriaga

  2. Department of Chemical Engineering, Texas A&M University, College Station, TX, 77843, USA

    Perla B. Balbuena

Authors
  1. Alnald Javier
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  2. Youn-Geun Kim
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  3. Jack Hess Baricuatro
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  4. Perla B. Balbuena
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  5. Manuel P. Soriaga
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Correspondence to Manuel P. Soriaga.

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Javier, A., Kim, YG., Baricuatro, J.H. et al. The Structure of Benzoquinone Chemisorbed on Pd(111): Simulation of EC-STM Images and HREELS Spectra by Density Functional Theory. Electrocatalysis 3, 353–359 (2012). https://doi.org/10.1007/s12678-012-0110-5

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  • DOI: https://doi.org/10.1007/s12678-012-0110-5

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