Journal of Chemical Physics, Vol.105, No.24, 10944-10953, 1996
Intermolecular Potential Effects in Trajectory Calculations of Collisions Between Large Highly Excited Molecules and Noble-Gases
Quasiclassical trajectory calculations have been applied to study intermolecular potential effects in the collisional deactivation of highly vibrationally excited aromatic molecules by noble gases. For benzene + helium and benzene + argon several potential functions of Lennard-Jones 12-6 and EXP-6 type were used. At low well depths epsilon (for benzene + helium) energy transfer is dominated by the exact shape of the intermolecular potential, especially of the repulsive part, whereas the dependence on E itself is less important. At higher well depths (for benzene + argon) the energy transfer parameters [Delta E] and [Delta E(2)] scale with epsilon and are much less sensitive to details of the interaction. New potential parameters based on experimental scattering data for the benzene + helium system are presented, which provide very good agreement with experimental energy transfer parameters for the deactivation of benzene and azulene by helium.
Keywords:DEPENDENT ENERGY-TRANSFER;VIBRATIONAL DEACTIVATION;POLYATOMIC-MOLECULES;TOLUENE SYSTEMS;GROUND-STATE;BATH GAS;AZULENE;TEMPERATURE;BENZENE;RELAXATION