A state-to-state dynamical study of the Br + H sub(2) reaction: comparison of quantum and classical trajectory results

• Published in: Physical chemistry chemical physics : PCCP Vol. 14; no. 37; pp. 13067 - 13075
• Main Authors: Panda, Aditya N, Herraez-Aguilar, Diego, Jambrina, Pablo G, Aldegunde, Jesus, Althorpe, Stuart C, Aoiz, FJavier
• Format: Journal Article
• Language: English
• Published: 01.08.2012
• Subjects: Cross sections; Dynamic tests; Endothermic reactions; Mathematical analysis; Physical chemistry; Quantum mechanics; Trajectories; Wave packets
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c2cp41825h

We present a detailed theoretical investigation of the dynamics corresponding to the strongly endothermic Br + H sub(2) (v= 0-1, j= 0) arrow right H + HBr reaction in the 0.85 to 1.9 eV total energy range. State-averaged and state-to-state results obtained through time-independent wave packet (TIWP) and time-independent quantum mechanical (TIQM) calculations and quasiclassical trajectories (QCT) are compared and analyzed. The agreement in the results obtained with both quantum mechanical results is very good overall. However, although QCT calculations reproduce the general features, their agreement with the QM results is sometimes only qualitative. The analysis of the mechanism based on state-averaged results turns out to be deceptive and conveys an oversimplified picture of the reaction consistent with a direct-rebound mechanism. Consideration of state-to-state processes, in contrast, unveils the existence of multiple mechanisms that give rise to a succession of maxima in the differential cross section (DCS). Such mechanisms correlate with different sets of partial waves and display similar collision times when analyzed through the time-dependent DCS.