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Journal Of Chemical Physics


Collisions of I-2 in the E(0(g)(+)) electronic state with CF4 molecules induce electronic energy transfer to the nearby D, beta, and D-' ion-pair states. Simulations of dispersed fluorescence spectra reveal collision-induced electronic energy transfer rate constants and final vibrational state distributions within each final electronic state. In comparison with earlier reports on I-2(upsilon(E)=0-2) collisions with He or Ar atoms, we find markedly different dynamics when I-2, excited to the same rovibronic states, collides with CF4. Final vibrational state distributions agree with the associated Franck-Condon factors with the initially prepared state to a greater degree than those found with He or Ar collision partners and suggest that internal degrees of freedom in the CF4 molecule represent a substantial means for accepting the accompanying loss of I-2 vibronic energy. Comparison of the E -> D transfer of I-2 excited to the J=23 and J=55 levels of the upsilon(E)=0 state reveals the onset of specific, nonstatistical dynamics as the available energy is increased above the threshold for excitation of the low frequency nu(2) bending mode of CF4. (c) 2006 American Institute of Physics.


This work is freely available courtesy of the American Institute of Physics.