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Title: Selectively breaking the O--H bond in HOD

Journal Article · · Journal of Chemical Physics; (USA)
DOI:https://doi.org/10.1063/1.458383· OSTI ID:7245586
; ;  [1]
  1. Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706 (US)

Vibrationally mediated photodissociation of HOD, in which one photon excites an O--H stretching vibration and another photon dissociates the vibrationally excited molecule, preferentially breaks the O--H bond for some photolysis wavelengths. Excitation of the third O--H stretching overtone (4{nu}{sub OH} ) of HOD followed by photolysis with a 239.5 or 266 nm photon produces at least 15 times more OD than OH product, as determined by laser induced fluorescence detection of both species. Dissociation of HOD(4{nu}{sub OH} ) with a 218.5 nm photon produces comparable amounts of OH and OD fragments. This large selectivity and strong dependence on the wavelength of the photolysis photon is consistent with qualitative models of vibrationally mediated photodissociation and with recent calculations.

OSTI ID:
7245586
Journal Information:
Journal of Chemical Physics; (USA), Vol. 92:1; ISSN 0021-9606
Country of Publication:
United States
Language:
English