An experimental and theoretical study of the bond selected photodissociation of HOD

Journal Article · Fri Mar 01 00:00:00 EST 1991 · Journal of Chemical Physics; (USA)

DOI:https://doi.org/10.1063/1.459777· OSTI ID:6255324

Vander Wal, R L; Scott, J L; Crim, F F ^[1]; Weide, K; Schinke, R ^[2]

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1. Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (US)
2. Max-Planck-Institut fuer Stroemungsforschung, D-3400 Goettingen, Federal Republic of Germany (DE)

Experimental and theoretical studies of the photodissociation of single vibrational states in HOD provide a qualitative and quantitative understanding of the dissociation dynamics and bond selectivity of this process. Vibrationally mediated photodissociation, in which one photon prepares a vibrational state that a second photon dissociates, can selectively cleave the O--H bond in HOD molecules containing four quanta of O--H stretching excitation. Dissociation of HOD(4{nu}{sub OH}) with 266 or 239.5-nm photons produces OD fragments in at least a 15 fold excess over OH, but photolysis of the same state with 218.5-nm photons produces comparable amounts of OH and OD. Wave packet propagation calculations on an {ital ab} {ital initio} potential energy surface reproduce these observations quantitatively. They show that the origin of the selectivity and its energy dependence is the communication of the initial vibrational state with different portions of the outgoing continuum wave function for different photolysis energies.

• OSTI ID: 6255324
• Journal Information: Journal of Chemical Physics; (USA), Vol. 94:5; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM COMPOUNDS
PHOTOLYSIS
WATER
DISSOCIATION
POTENTIAL ENERGY
VIBRATIONAL STATES
WAVE FUNCTIONS
CHEMICAL REACTIONS
DECOMPOSITION
ENERGY
ENERGY LEVELS
EXCITED STATES
FUNCTIONS
HYDROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
400500* - Photochemistry