Absolute vibrational spectra of the electrochemical H/Pt and H/Pt(100) interfaces in the under- and overpotential ranges are measured by ir-vis sum frequency generation. The vibrational signature of the underpotential-deposited hydrogen is structure sensitive and is related to its bonding configuration and to the water molecules located in the double layer region. A new hydrogen adspecies, presumed to be the intermediate for the hydrogen evolution reaction, shows up in the overpotential range, with a similar vibrational fingerprint on both surfaces.
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Peremans et al. (1994) studied this question.
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