Stark effect or coverage dependence? Disentangling the EC-SEIRAS vibrational shift of sulfate on Au(111)

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Title: Stark effect or coverage dependence? Disentangling the EC-SEIRAS vibrational shift of sulfate on Au(111)
Authors: Pfisterer, Jonas H.K. | Zhumaev, Ulmas E. | Cheuquepán, William | Feliu, Juan M. | Domke, Katrin F.
Research Group/s: Electroquímica de Superficies | Grupo de Espectroelectroquímica y Modelización (GEM)
Center, Department or Service: Universidad de Alicante. Departamento de Química Física | Universidad de Alicante. Instituto Universitario de Electroquímica
Keywords: Stark effect | Coverage dependence | Electrochemical surface science | EC-SEIRAS | Vibrational shift | Sulfate | Au(111)
Knowledge Area: Química Física
Issue Date: 5-Dec-2018
Publisher: AIP Publishing
Citation: The Journal of Chemical Physics. 2019, 150: 041709. doi:10.1063/1.5047941
Abstract: Infrared spectroscopy is a widely employed analytical tool in (electrochemical) surface science as the spectra contain a wealth of information about the interaction of interfacial adsorbates with their environment. Separating and quantifying individual contributions, for example, of co-adsorbates, the substrate or electric field effects, on the overall spectral response, however, is often non-trivial as the various interactions manifest themselves in similar spectral behavior. Here, we present an experimental approach to differentiate between and quantify potential-induced coverage dependence and field-related Stark effects observed in a sulfate band shift of 93.5 ± 1.5 cm−1/V in electrochemical infrared spectra of the showcase sulfate/Au(111) interface. In combination with a simple linear model equation used to describe the potential-induced peak shift of the sulfate stretch vibration, we determine the coverage dependence contribution to be 15.6 ± 1.2 cm−1/θSO and the Stark effect to amount to 75.6 ± 2.7 cm−1/V. Our work provides a novel route to gain fundamental insight into interfacial adsorbate interactions in electrochemical surface science.
Sponsor: J.H.K.P. and K.F.D. gratefully acknowledge financial support by the Max Planck Graduate Center with the Johannes Gutenberg University Mainz (MPGC). U.E.Z. is grateful for financial support from the Alexander von Humboldt Foundation. J.M.F. thanks MCINN-FEDER (Spain) for support through Project No. CTQ2016-76221-P. K.F.D. acknowledges generous support through the Emmy Noether Program of the Deutsche Forschungsgemeinschaft (No. DO1691/1-1) and through the “Plus 3” Program of the Boehringer Ingelheim Foundation.
URI: http://hdl.handle.net/10045/87347
ISSN: 0021-9606 (Print) | 1089-7690 (Online)
DOI: 10.1063/1.5047941
Language: eng
Type: info:eu-repo/semantics/article
Rights: © 2019 Author(s). Published under license by AIP Publishing
Peer Review: si
Publisher version: https://doi.org/10.1063/1.5047941
Appears in Collections:INV - GEM - Artículos de Revistas
INV - EQSUP - Artículos de Revistas

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