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Temperature dependence of vibrational energy transfer in NH/sub 3/ and H/sub 2/ /sup 18/O

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5484626

The V..-->..T, R relaxation rate for NH/sub 3/ (..nu../sub 2/) has been studied from 198 to 398 /sup 0/K by the method of laser-excited vibrational fluorescence. The self-deactivation rate constant decreases from 4.9 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/ at 198 /sup 0/K to 2.7 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/ at 398 /sup 0/K. The rate constants for deactivation by He, Ar, N/sub 2/, and O/sub 2/ are much smaller and show a weak temperature dependence in the opposite direction. For H/sub 2/ /sup 18/O the vibrational relaxation rates of the coupled ..nu../sub 1/, ..nu../sub 3/ stretching level manifold and of the 2..nu../sub 2/ bending level have been studied from 250 to 400 /sup 0/K. The ..nu../sub 1/, ..nu../sub 3/ self-deactivation rate goes from 3.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/ at 250 /sup 0/K to 2.0 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/ at 400 /sup 0/K. For 2..nu../sub 2/ it goes from 1.2 x 10/sup -10/ to 7.8 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. The temperature depencence of the deactivation of both levels by He and Ar is much weaker and the rates are several hundred times slower. CO/sub 2/ deactivates ..nu../sub 1/, ..nu../sub 3/ about 50 times faster than He or Ar at 293 /sup 0/K.

Research Organization:
Department of Chemistry, University of California, Berkeley, California 94720
OSTI ID:
5484626
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 72:4; ISSN JCPSA
Country of Publication:
United States
Language:
English