Energy transfer between polyatomic molecules II: Energy transfer quantities and probability density functions in benzene, toluene, p-xylene, and azulene collisions.
Collisional energy transfer, CET, is of major importance in chemical, photochemical, and photophysical processes in the gas phase. In Paper I of this series (J. Phys. Chem. B 2005, 109, 8310) we have reported on the mechanism and quantities of CET between an excited benzene and cold benzene and Ar bath. In the present work, we report on CET between excited toluene, p-xylene, and azulene with cold benzene and Ar and on CET of excited benzene with cold toluene, p-xylene, and azulene. We compare our results with those of Paper I and report average vibrational, rotational, and translational energy quantities, <DeltaE>, transferred in a single collision. We discuss the effect of internal rotation on CET and the identity of the gateway modes in CET and the relative role of vibrational, rotational, and translational energies in the CET process, all that as a function of temperature and excitation energy. Energy transfer probability density functions, P(E,E'), for the various systems are reported and the shape of the curves for various systems and initial conditions is discussed. The major findings for polyatomic-polyatomic collisions are: CET takes place mainly via vibration-to-vibration energy transfer assisted by overall rotations. Internal free rotors in the excited molecule hinder energy exchange while in the bath molecule they do not. Energy transfer at low temperatures and high temperatures is more efficient than that at intermediate temperatures. Low-frequency modes are the gateway modes for energy transfer. Vibrational temperatures affect energy transfer. The CET probability density function, P(E,E'), is convex at low temperatures and can be concave at high temperatures. A mechanism that explains the high values of <DeltaE(a)> and the convex shape of P(E,E') is that in addition to short impulsive collisions there are chattering collisions where energy is transferred in a sequence of short encounters during the lifetime of the collision complex. This also leads to the observed supercollision tail at the down wing of P(E,E'). Polyatomic-Ar collisions show mechanistic similarities to polyatomic-polyatomic collisions, but there are also many dissimilarities: internal rotations do not inhibit energy transfer, P(E,E') is concave at all temperatures, and there is no contribution of chattering collisions.
Bernshtein
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Department of Chemistry, Technion-Israel institute of Technology, Haifa 32000, Israel.
Oref
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