Journal of Chemical Physics, Vol.109, No.16, 6736-6744, 1998
State-to-state vibrational relaxation from levels at state densities up to 2.3 states per cm(-1) in p-difluorobenzene
Collision-induced vibrational energy transfer has been studied from three vibrational levels at intermediate state density in S-1 p-difluorobenzene in a supersonic foe jet expansion. Transfer was studied from the 5(1) (E-vib = 818 cm(-1); rho(vib) = 0.6 per cm(-1)), 29(2) (E-vib = 876 cm(-1); rho(vib) = 0.6 per cm(-1)), and 5(1)8(2) (E-vib = 1179 cm(-1); rho(vib) = 2.3 per cm(-1)) levels. The collision partners include a range of monatomics, diatomics, and polyatomics for 5(1) and 29(2). Hydrogen was the collision partner for 5(1)8(2). For 29(2), transfers involving multiple changes in vibrational quanta are important, and generally such transfers dominate. This behavior is different from that observed at low state densities but is analogous to what has been observed previously at intermediate state densities in;p-difluorobenzene [Mudjijono and W. D. Lawrance, J. Chem. Phys. 108, 4877 (1998)]. There is a suggestion in the data for c-propane and ethane that transfer to vibrational modes of these collision partners is occurring. 5(1) shows very inefficient relaxation. With the exception of N-2, there is no evidence in the spectra for significant transfer via channels involving multiple changes in vibrational quanta. The state-to-state branching ratios for transfer from 5(1)8(2) were essentially in quantitative agreement with those expected based on transfer from 8(2). It appears that the in-plane mode v(5), and combinations involving low frequency modes with v(5), behave qualitatively differently to the lower frequency, out-of-plane modes. The lower frequency, out-of-plane modes change their state-to-state relaxation preferences with increasing vibrational state density, with multiple quantum changes becoming preferred, while the higher frequency in-plane v(5) retains the state-to-state preferences seen at low state densities.
Keywords:COLLISIONAL ENERGY-TRANSFER, MOLECULES, DEACTIVATION;FLUORESCENCE, EXCITATION, BENZENE, FLOW