Vibrationally mediated photodissociation of hydrogen peroxide
Vibrationally mediated photodissociation is a means of studying the spectroscopy of bound vibrational overtone states and of probing the electronic photodissociation dynamics of highly vibrationally excited molecules. In these experiments, a highly vibrationally excited hydrogen peroxide molecule prepared by initial excitation in the region of the third (4..nu../sub OH/) or fourth (5..nu../sub OH/) overtone of the OH stretching vibration absorbs an additional photon to dissociate to OH fragments whose individual quantum state populations are measured by laser induced fluorescence. This technique is a means of obtaining excitation spectra for bound highly vibrationally excited states and confirms the accuracy of a model that incorporates the role of the torsional vibration in the vibrational overtone spectroscopy. The photodissociation dynamics of highly vibrationally excited molecules are substantially different from those observed for dissociation by single photons of comparable or greater energy. Approximately 11% of the OH fragments formed in the vibrationally mediated photodissociation through 4..nu../sub OH/ are vibrationally excited as compared to an unobservable amount (less than or equal to2%) in the single photon ultraviolet dissociation.
- Research Organization:
- Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706
- OSTI ID:
- 6146923
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 87:10
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
HYDROGEN PEROXIDE
DISSOCIATION
PHOTOLYSIS
VIBRATIONAL STATES
EXCITED STATES
MULTI-PHOTON PROCESSES
CHEMICAL REACTIONS
DECOMPOSITION
ENERGY LEVELS
HYDROGEN COMPOUNDS
OXYGEN COMPOUNDS
PEROXIDES
PHOTOCHEMICAL REACTIONS
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory