Trajectory approach to the mode-selected photodissociation of CS2

Through the study of photodissociation events in the CS(2) molecule that originate in various selected vibrational modes, but terminate in the same final predissociation state, we looked for the evidence that photodissociation processes can depend on the initial conditions. Such dependence would not occur within RRKM theory, because of its statistical assumptions. The experimental results were compared with trajectory calculations in normal mode coordinates, in which initial conditions were given in terms of coordinates and momenta. We have found that the photodissociation rate for events originating in the combination nu(1), nu(2) mode is higher than that for events from the pure nu(2) mode, and shows a large variation along the vibrational progression. The experimental observations agree with the trajectory calculations. In addition, the trajectory calculations predict that photodissociation events initiated at small values of the vibrational coordinates result in larger dissociation rates at low excess energy above the dissociation limit, while events from large values of the coordinates result in larger dissociation rates at high excess energies.