Journal of Physical Chemistry A, Vol.120, No.27, 5187-5196, 2016
Chemical Dynamics Simulations of Intermolecular Energy Transfer: Azulene + N-2 Collisions
Chemical dynamics simulations were performed to investigate collisional energy transfer from highly vibrationally excited azulene (Az*) in a N-2 bath. The intermolecular potential between Az and N-2, used for the simulations, was determined from MP2/6-31+G* ab initio calculations. Az* is prepared with an 87.5 kcal/mol excitation energy by using quantum micro canonical sampling, including its 95.7 kcal/mol zero-point energy. The average energy of Az* versus time, obtained from the simulations, shows different rates of Az* deactivation depending on the N-2 bath density. Using the N-2 bath density and Lennard-Jones collision number, the average energy transfer per collision was obtained for Az* as it is collisionally relaxed. By comparing versus the bath density, the single collision limiting density was found for energy transfer. The resulting , for an 87.5 kcal/mol excitation energy, is 0.30 +/- 0.01 and 0.32 +/- 0.01 kcal/mol for harmonic and anharmonic Az potentials, respectively. For comparison, the experimental value is 0.57 +/- 0.11 kcal/mol. During Az* relaxation there is no appreciable energy transfer to Az translation and rotation, and the energy transfer is to the N-2 bath.