Chemical Physics Letters, Vol.343, No.5-6, 581-587, 2001
Asymmetric stretch vibrational energy relaxation of OClO in liquid water
Motivated by a femtosecond experiment and a study of the vibrational energy relaxation (VER) of asymmetric stretch excited OC1O(aq), molecular dynamics (MD) simulations of OC1O(aq) are used to determine force correlation functions (CF), important in the VER of OCIO(aq). Together with a golden rule formula, these simulations are utilized to estimate the lifetime of the OC1O asymmetric stretch mode, excited with one quantum. The calculated lifetime of 9 ps agrees well with the model of Poulsen and coworkers, thereby supporting the findings of their paper, that the geminate recombination of OC1O primarily induces excitations in the OC1O asymmetric stretch mode.