Optical analysis of thin-layer electrochemical cells for infrared spectroscopy of adsorbates

The optical properties of a thin-layer electrochemical cell have been quantitatively analyzed with special consideration given to optimizing the experimental sensitivity of infrared reflection-absorption spectroscopy (IRRAS) to the typically weak infrared absorption due to an adsorbate on the workin...

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Bibliographic Details
Published inSurface science Vol. 197; no. 1; pp. 44 - 66
Main Authors Bethune, D.S., Luntz, A.C., Sass, J.K., Roe, D.K.
Format Journal Article
LanguageEnglish
Published Lausanne Elsevier B.V 1988
Amsterdam Elsevier Science
New York, NY
Subjects
Chemistry
Electrochemistry
Exact sciences and technology
General and physical chemistry
Infrared spectrometry
Reflection spectrometry
Fourier transformation
Theoretical study
Electrode electrolyte interface
Instrumentation
Molecular vibration
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Summary:The optical properties of a thin-layer electrochemical cell have been quantitatively analyzed with special consideration given to optimizing the experimental sensitivity of infrared reflection-absorption spectroscopy (IRRAS) to the typically weak infrared absorption due to an adsorbate on the working electrode surface. It is found that the sensitivity is dramatically affected by interference effects in the cell, and that such effects may be exploited to increase the fractional change in reflectivity ( ΔR R ) due to the adsorbate. In addition, these effects strongly influence the lineshapes in vibrational spectra and can even reverse the sign of the reflectivity change. Some of the predicted optical properties have been experimentally observed using a thin-layer electrochemical cell and a tunable infrared laser to study CO adsorbed on an Pt electrode.
ISSN:0039-6028
1879-2758
DOI:10.1016/0039-6028(88)90572-9