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The H + OCS hot atom reaction - CO state distributions and translational energy from time-resolved infrared absorption spectroscopyTime-resolved infrared diode laser spectroscopy has been used to probe CO internal and translational excitation from the reaction of hot H atoms with OCS. Product distributions should be strongly biased toward the maximum 1.4 eV collision energy obtained from 278 nm pulsed photolysis of HI. Rotations and vibrations are both colder than predicted by statistical density of states theory, as evidenced by large positive surprisal parameters. The bias against rotation is stronger than that against vibration, with measurable population as high as v = 4. The average CO internal excitation is 1920/cm, accounting for only 13 percent of the available energy. Of the energy balance, time-resolved sub-Doppler line shape measurements show that more than 38 percent appears as relative translation of the separating CO and SH fragments. Studies of the relaxation kinetics indicate that some rotational energy transfer occurs on the time scale of our measurements, but the distributions do not relax sufficiently to alter our conclusions. Vibrational distributions are nascent, though vibrational relaxation of excited CO is unusually fast in the OCS bath, with rates approaching 3 percent of gas kinetic for v = 1.
Document ID
19930066814
Acquisition Source
Legacy CDMS
Document Type
Reprint (Version printed in journal)
External Source(s)
Authors
Nickolaisen, Scott L.
(U.S. Military Academy, West Point, NY; JPL, Pasadena CA, United States)
Cartland, Harry E.
(U.S. Military Academy West Point, NY, United States)
Date Acquired
August 16, 2013
Publication Date
July 15, 1993
Publication Information
Publication: Journal of Chemical Physics
Volume: 99
Issue: 2
ISSN: 0021-9606
Subject Category
Atomic And Molecular Physics
Accession Number
93A50811
Funding Number(s)
CONTRACT_GRANT: DAAL03-91-C-0034
Distribution Limits
Public
Copyright
Other

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