Vibrationally mediated photodissociation of H2O2 (4vOH): rotational state dependent photodissociation cross sections and vibrational state mixing
✍ Scribed by M. Brouard; R. Mabbs
- Publisher
- Elsevier Science
- Year
- 1993
- Tongue
- English
- Weight
- 773 KB
- Volume
- 204
- Category
- Article
- ISSN
- 0009-2614
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✦ Synopsis
A reinvestigation of the vibrationaBy mediated photodissociation spectrum of the 3rd OH stretching overtone (411cu) of jetcooled HsO,, first observed by Crim and co-workers, reveals anomalous double resonance spectral intensities compared with those observed via hi&-resolution absorption spectroscopy. The origin of these intensity perturbations is traced to & level dependent variations in the photodissociation cross section, uoo, out of the intermediate overtone state. The photofragment OH( X, v= 0) rotational state distribution generated by photodissociation of Hz02 (4~ ou, JU = 2sa) ,has also been determined. Combined with the relative cross-section data, these results imply that delocalization of the overtone state wavefunction into wideamplitude O-O stretching regions of the ground state is profoundly influenced by parent molecular rotation, primarily about the a and b axes. The intermediate state with J'= 0 is shown to be much more highly localized, and hence more likely to display mode selective bebaviour, than its J'> 0 counterparts.