Building transition probabilities for any condition using scaled cumulative energy transfer functions in H2O-H2O collisions.

RAÚL A. BUSTOS MARÚN, EDUARDO A. CORONADO Y JUAN C. FERRERO

Orléans-France

Simposio; 19th International Symposium on Gas Kinetics; 2006

Members of the Laboratorie de Combustion et Systèmes Rèactifs and Université d'Oléans

The energy transfer process between highly vibrationally excited H2O in a gas bath of H2O in thermal equilibrium at different internal energies and temperatures has been studied by classical trajectory calculations using the ab initio PJT2 and VRT(MCY) intra and intermolecular potentials respectively.As in previous work, the results are analyzed using a cumulative probability distribution Q(∆E) of the amount of energy transfered obtained by direct count of the number of trajectories that transfer an amount of energy equal or greater than a certain amount <∆E>.The transition porbabilities are obtained by differentiation of the respective cumulative function. In this work we apply this treatment for both up and down transitions, which allow us to apply more rigurous detailed balance contrains. Scaling of Q(∆E) in terms of the mean down and up energy transfer transfered for each group of trajectories, results in a unique distribution. This fact and the use of detailed balance arguments, allow us to build the whole P(E´,E), for any condition by knowing only one parameter i.e. the value of <∆E all > for a given temperatue and internal energy.