Two-color vibrationally mediated photodissociation, in which one photon excites an overtone vibration and a second photon of a different wavelength dissociates the highly vibrationally excited molecule prepared by the first photon, is a means of investigating the role of vibrational excitation in photodissociation and of obtaining vibrational overtone excitation spectra. Application of this scheme to nitric acid (HONO2) involves exciting the third OH stretching overtone vibration (4vOH), photodissociating the vibrationally excited molecule with 355-nm light, and detecting the OH fragment using laser-induced fluorescence. These measurements show that most of the OH products are vibrationally unexcited and that about a quarter of the available energy goes into relative translation. The vibrational overtone excitation spectrum has congested P-, Q-, and R-branch rotational structure that forms a 50-cm-1-wide band.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry