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Absolute Surface Coverage Measurement Using a Vibrational Overtone



A C. Pipino, J P. Hoefnagels, N Watanabe


Sub-monolayer absolute surface number densities are obtained by cavity ring-down spectroscopy (CRDS) for three haloethylenes with differing molecular symmetries on silica using the first C-H stretching overtones. Gas-phase CRDS measurements provide absolute absorption cross sections, while evanescent wave CRDS (EW-CRDS) measurements provide polarized absolute adsorbate spectra. The absolute surface number densities are found from conservation of the integrated band intensities with adsorption along with a measure of surface orientation as derived from the polarization anisotropy. The first stretching C-H overtones of trichloroethylene (TCE), cis-dichloroethylene (c-DCE), and trans-dichloroethylene (t-DCE) occurring around 6050 cm-1 are probed with the idler of a seeded optical parametric amplifier having a 0.075 cm-1 linewidth. The EW-CRDS measurements employ a fused-silica monolithic folded resonator with a peak finesse of .28,500. An independent determination of the absolute surface coverage of TCE on a SiO2 surface is also obtained by mass-spectrometer-based uptake measurements. The sensitivity of EW-CRDS for TCE detection with an unclad resonator is found to be comparable to that obtained with a long-effective-path-length waveguide having a TCE-enriching polysiloxane coating.
Journal of Chemical Physics
No. 6


absolute coverage, absolute cross-section, absolute intensity, cavity ring-down, dichloroethylene, evanescent waves, overtones, trichloroethylene, vibrational spectroscopy


Pipino, A. , Hoefnagels, J. and Watanabe, N. (2004), Absolute Surface Coverage Measurement Using a Vibrational Overtone, Journal of Chemical Physics (Accessed June 21, 2024)


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Created February 1, 2004, Updated February 17, 2017