A six-dimensional wave packet study of the vibrational overtone induced decomposition of hydrogen peroxide

• Published in: The Journal of chemical physics 2012-04, Vol.136 (16), p.164314-164314-5
• Main Authors: Wang, Chunrui, Zhang, Dong H., Skodje, Rex T.
• Format: Article
• Language: English
• Subjects: Angular momentum; Autocorrelation functions; Dynamics; Hydrogen peroxide; Mathematical analysis; Simulation; Survival; Wave packets
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4705755

A converged quantum wave packet study is presented for the unimolecular reaction HOOH → OH+OH induced by the fifth OH-overtone excitation employing an ab initio potential energy surface. All six internal vibrational degrees of freedom are explicitly represented in this simulation for total angular momentum zero. It is found that the decay of the survival probability and of the autocorrelation function is non-exponential and that the long time dynamics is likely due to the superposition of a number of resonance states. The simulated overtone spectrum and rotational product distribution is in good agreement with experimental measurements. It is concluded that: (1) the reaction dynamics is non-statistical on a 30 ps timescale, (2) the observed line width is roughly a factor of 1.7 larger than implied by the reactive lifetimes suggesting that a significant portion of the linewidth is due to intramolecular vibrational energy relaxation, and (3) the quantum reaction rate is suppressed by about a factor of two relative to its classical counterpart.