Mode-to-mode energy transfer in collisions between S/sub 1/ state aniline and Ar, CO, CO/sub 2/, C/sub 2/H/sub 2/, C/sub 3/H/sub 4/, OCS, Xe, and N/sub 2/O
SVL fluorescence spectroscopy was used to study V-T,R processes in collisions of 0/sup 0/ aniline with Ar, Xe, CO, CO/sub 2/, OCS, N/sub 2/O, acetylene, and allene. Populations were monitored in eight aniline vibronic levels. To first order, the experimental propensity rules for single-collision up pumping of 0/sup 0/ aniline to these levels are identical for all collision gases. An exception is the unusually large rate constant for population of the 1/sup 1/ level in collisions with allene, whose 11/sub 1/ level is nearly degenerate with the I/sup 1/ level in aniline; this may be evidence of an important V--V process. The endoergic up-pumping probabilities correlate well with ..mu../sup 1//sup ///sup 2/ for rare gas partners, but poorly for the other collision gases. No evidence is found that V-R processes contribute substantially to the rate constants for aniline in collision with CO or the polyatomic gases. The quantitative propensity rules provide a basis for a mode-to-mode collisional energy transfer theory, developed by Freed, in which the observed large V-T,R cross sections arise as a direct consequence of the intramolecular intermode coupling within large molecules such as aniline.
- Research Organization:
- Department of Chemistry and Ames Laboratory, U.S. Department of Energy, Iowa State University, Ames, Iowa 50011
- OSTI ID:
- 6876649
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 80:11
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ACETYLENE
MOLECULE-MOLECULE COLLISIONS
ALLENE
ANILINE
ATOM-MOLECULE COLLISIONS
ARGON
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXYSULFIDE
NITROUS OXIDE
XENON
ENERGY TRANSFER
FLUORESCENCE SPECTROSCOPY
ALKYNES
AMINES
AROMATICS
ATOM COLLISIONS
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COLLISIONS
DIENES
ELEMENTS
EMISSION SPECTROSCOPY
FLUIDS
GASES
HYDROCARBONS
MOLECULE COLLISIONS
NITROGEN COMPOUNDS
NITROGEN OXIDES
NONMETALS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
POLYENES
RARE GASES
SPECTROSCOPY
SULFUR COMPOUNDS
640304* - Atomic
Molecular & Chemical Physics- Collision Phenomena