Journal of Physical Chemistry A, Vol.102, No.44, 8505-8509, 1998
Vibrational deactivation of highly excited hexafluorobenzene
Highly excited hexafluorobenzene (HFB) molecules in the electronic ground state were prepared by infrared multiphoton absorption by CO2 laser pumping using:the P(38) line at 1029.43 cm(-1). The vibrational deactivation of the highly excited HFB by monatomic collider gases was monitored by time-resolved infrared fluorescence (IRF). Deactivation measurements were made for the noble gas colliders He, Ne, Ar, Kr, and Xe. The bulk average energy transferred per collision, [Delta E], for-these colliders was found to increase from He through to Ar; however it subsequently decreased from Ar through to Xe. This is different than the trend found in the quasiclassical trajectory calculations by Lenzer et al., which predict a decrease in the average energy transferred per collision from He to Ar to Xe. (Calculations were not reported for Ne and Kr.) However, similar trends in related energy-transfer parameters have been reported for the deactivation of C6F14 and C8F18 by the same series of five noble gases. A comparison is made with previous experimental measurements for the colliders He and Ar which were obtained using UV excitation of the HFB. For the same monatomic colliders, the [Delta E] values for HFB are much greater than those for the closely related aromatics, benzene, toluene, and pyrazine.
Keywords:COLLISIONAL ENERGY-TRANSFER, IR-MULTIPHOTON ABSORPTION;HALOGENATED AROMATIC-MOLECULES, RESOLVED INFRARED FLUORESCENCE;LARGE POLYATOMIC-MOLECULES, PLANE VIBRATIONS, FORCE-FIELD;RELAXATION, POPULATIONS, BENZENE