Energy transfer of highly vibrationally excited azulene: collisions between azulene and krypton.
The energy-transfer dynamics between highly vibrationally excited azulene molecules and Kr atoms in a series of collision energies (i.e., relative translational energies 170, 410, and 780 cm(-1)) was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. "Hot" azulene (4.66 eV internal energy) was formed via the rapid internal conversion of azulene initially excited to the S4 state by 266-nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited or hot azulene. At low enough collision energies an azulene-Kr complex was observed, resulting from small amounts of translational to vibrational-rotational (T-VR) energy transfer. T-VR energy transfer was found to be quite efficient. In some instances, nearly all of the translational energy is transferred to vibrational-rotational energy. On the other hand, only a small fraction of vibrational energy is converted to translational energy (V-T). The shapes of V-T energy-transfer probability density functions were best fit by multiexponential functions. We find that substantial amounts of energy are transferred in the backward scattering direction due to supercollisions at high collision energies. The probability for supercollisions, defined arbitrarily as the scattered azulene in the region 160 degrees <theta<180 degrees and DeltaEd>2000 cm(-1) is 1% and 0.3% of all other collisions at collision energies 410 and 780 cm(-1), respectively.
Institute of Atomic and Molecular Sciences, Academia Sinica, P. O. Box 23-166, Taipei 10617, Taiwan.
Chen-Lin
CL
Liu
Hsu-Chen
HC
Hsu
Jia-Jia
JJ
Lyu
Chi-Kung
CK
Ni