화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.105, No.12, 2731-2737, 2001
Predominance of nonequilibrium dynamics in the photodissociation of ketene in the triplet state
The photodissociation of ketene is studied using direct surface-hopping classical trajectories where the energy and gradient are computed on the fly by means of state-averaged complete active space self-consistent field with a double-zeta polarized basis set. Three low-lying electronic states, singlets S-0 and S-1 and triplet T-1, are involved in the process of photodissociation of triplet state ketene. We propagated a trajectory, starting at the Franck-Condon geometry on S-1, and branched it out into many child trajectories every time the propagating potential energy surface (PES) crossed with another PES. The major photodissociation pathway to the triplet products was found to be S-1 --> S-0 --> T-1 --> CH2((XB1)-B-3) + CO(X(1)Sigma (+)). It has been found that (1) the S-0-T-1 nonadiabatic transition creates the T-1 species nonstatistically at restricted regions of phase space and (2) a large fraction of the T-1 species thus created dissociates almost immediately, leaving no time for equilibration of internal degrees of freedom. Whether a specific T-1 trajectory dissociates fast or not is determined by the amount of C-C stretch vibration at the S-0-T-1 branch point. In essence, the above observations suggest strongly that the T-1 photodissociation process is highly nonstatistical, thus making equilibrium-based statistical theories inapplicable for computing the dissociation rate.