Quantum scattering calculation of the O(1D)+HBr reaction

Abstract

Three-dimensional time-dependent quantum wave packet calculation for the O( 1 D)ϩHBr reaction has been carried out using an accurate ab initio global potential energy surface ͓K. A. Peterson, J. Chem. Phys. 113, 4598 ͑2000͔͒. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.

The reagent vibrational excitation effect on the stereodynamics of the reaction O(1D)+ HBr → OH + Br

“…Compared with other reactions, the title reaction has a deep well on the singlet PES which leads to a long-lifetime intermediate complex. Moreover, Tang et al [12] have also proved that the ab initio calculations of HOBr are nearly identical to previous results of HOCl [19,20] and the stability and reliability of the calculated results below can be guaranteed [21,22] with high vibrational levels. The calculation method of QCT is similar to that described in Refs.…”

“…Previous theoretical studies provided the impetus for the development of theoretical methods to simulate the measured profiles and to provide an insight into that information about the stereodynamics, which has not been obtained yet. Recently, using the time-dependent wave packet methods, Tang et al [12] have computed the reaction probabilities and thermal rate constants, which are nearly independent of temperature.…”

Vibrational excitation influence on the H + BrO → HBr + O reaction: a quasi-classical trajectory investigation

“…[1][2][3][4][5] One channel of the HOBr system, the O + HBr ¡ OH + Br reaction, has been extensively investigated for its kinetics and mechanism. For experimental cases, Wine et al performed time-resolved resonance fluorescence detection with pulsed laser photolysis to determine the rate constant and the yield of the product.…”

Effect of the isotope substitution on the stereodynamics for O+H(D)Br --> OH(D)+Br reactions

“…On the experimental side, Ruscic and Berkowitz have successfully ciphered the heat of formation of HOBr and the dissociation energy of HO-Br [14]. From the theoretical point of view, Tang et al [15] have successfully employed the three-dimensional time-dependent quantum wave packet method to study the scalar properties of the reaction such as initial state-selected reaction probabilities, reactive cross sections and thermal rate constant. Additionally, the potential energy surface (PES) for the X 1 A ′ singlet state of HOBr system was recently constructed by Peterson [16].…”