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Climbing the Vibrational Ladder to Probe the OH Stretch of HNO3 on Silica



A C. Pipino, Marcin Michalski


The first and second OH-stretching overtones of HNO3 adsorbed on atomically smooth amorphous SiO2 have been probed by evanescent wave cavity ring-down spectroscopy (EW-CRDS) using a broadband high-finesse total-internal-reflection-ring resonator. In contrast to the OH-stretching fundamental, the overtone spectra reveal relatively sharp features under conditions of extensive H-bonding. Based on a comparison with calculated vibrational frequencies, we find HNO3 exists predominantly as the HNO3-H2O complex on the surface under ambient conditions. EW-CRDS yields polarized, absolute absorption spectra for overtone and combination transitions at sub-monolayer coverage, enabling unparalleled spectroscopic studies of monolayers, thin films, and nano-scale materials. The TIR-ring resonator in particular permits facile exploration of the visible and near-IR regions with a single optical configuration.
Journal of Physical Chemistry C


absorption, cavity ring-down, evanescent wave, finesse, overtone, resonator


Pipino, A. and Michalski, M. (2008), Climbing the Vibrational Ladder to Probe the OH Stretch of HNO<sub>3</sub> on Silica, Journal of Physical Chemistry C (Accessed April 23, 2024)
Created October 16, 2008