Asymmetric stretch vibrational energy relaxation of OClO in liquid water

• Published in: Chemical physics letters Vol. 343; no. 5; pp. 581 - 587
• Main Authors: Poulsen, Jens, Nymand, Thomas M., Keiding, Søren R.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 10-08-2001; Elsevier Science
• Subjects: Atomic and molecular physics; Exact sciences and technology; Intensities and shapes of molecular spectral lines and bands; Molecular properties and interactions with photons; Oscillator and band strengths, lifetimes, transition moments, and franck-condon factors; Physics; Lifetime; Inorganic compounds; Aqueous solutions; Digital simulation; Vibrational modes; Molecular dynamics method; Vibrational relaxation; Chlorine oxides; Vibrationally excited state; Triatomic molecule
• ISSN: 0009-2614; 1873-4448
• DOI: 10.1016/S0009-2614(01)00745-X

Motivated by a femtosecond experiment and a study of the vibrational energy relaxation (VER) of asymmetric stretch excited OClO(aq), molecular dynamics (MD) simulations of OClO(aq) are used to determine force correlation functions (CF), important in the VER of OClO(aq). Together with a golden rule formula, these simulations are utilized to estimate the lifetime of the OClO 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 OClO primarily induces excitations in the OClO asymmetric stretch mode.