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U.S. Department of Energy
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Determination of stepsize parameters for intermolecular vibrational energy transfer: Progress report, May 1, 1987-April 30, 1988

Technical Report ·
OSTI ID:6995036

Intermolecular vibrational energy transfer for highly excited polyatomic molecules is involved in any mechanism in which excitation energy is required (pyrolysis) or in which energy must be removed from a hot source (cooling). The average energy removed per collision, , is a useful quantity to compare efficiency for energy transfer. The objectives of this work are: to determine the dependence of on excitation energy and on the molecular complexity (number of vibrational modes) of substrate and deactivator; to assess the importance of intermolecular attractions (complex formation) on vibrational energy transfer; to obtain detailed information on the energy distribution after collision and to evaluate the importance of on high-temperature unimolecular reactions. This information will be obtained by monitoring the time dependence of the infrared emission, ultraviolet absorption, refractive index and pressure. The results from these complementary techniques will be benchmarked with values from previous studies on the relaxation of chemically activated alkyl and fluoroalkyl radicals. Trajectory calculations simulating energy transfer are being performed for ''generic'' substrate/deactivator pairs to provide additional details and insight on the important parameters. Model calculations are also being performed to determine the feasibility of obtaining information from experimental data for high-temperature unimolecular reactions.

Research Organization:
Iowa Univ., Iowa City (USA)
DOE Contract Number:
FG02-87ER13700
OSTI ID:
6995036
Report Number(s):
DOE/ER-13700-1; ON: DE88010904
Country of Publication:
United States
Language:
English