In:
The Journal of Chemical Physics, AIP Publishing, Vol. 150, No. 4 ( 2019-01-28)
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.
Type of Medium:
Online Resource
ISSN:
0021-9606
,
1089-7690
Language:
English
Publisher:
AIP Publishing
Publication Date:
2019
detail.hit.zdb_id:
3113-6
detail.hit.zdb_id:
1473050-9
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