New Stress Test for Ring Polymer Molecular Dynamics: Rate Coefficients of the O(3P) + HCl Reaction and Comparison with Quantum Mechanical and Quasiclassical Trajectory Results

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2019-09, Vol.123 (37), p.7920-7931
• Main Authors: Menéndez, M, Jambrina, P. G, Zanchet, A, Verdasco, E, Suleimanov, Y. V, Aoiz, F. J
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.9b06695

In the past decade, ring polymer molecular dynamics (RPMD) has emerged as a very efficient method to determine thermal rate coefficients for a great variety of chemical reactions. This work presents the application of this methodology to study the O­(3P) + HCl reaction, which constitutes a stringent test for any dynamical calculation due to rich resonant structure and other dynamical features. The rate coefficients, calculated on the 3A′ and 3A″ potential energy surfaces (PESs) by Ramachandran and Peterson [ J. Chem. Phys. 2003, 119, 9590 ], using RPMD and quasiclassical trajectories (QCT) are compared with the existing experimental and the quantum mechanical (QM) results by Xie et al. [ J. Chem. Phys. 2005 122, 014301 ]. The agreement is very good at T > 600 K, although RPMD underestimates rate coefficients by a factor between 4 and 2 in the 200–500 K interval. The origin of these discrepancies lies in the large contribution from tunneling on the 3A″ PES, which is enhanced by resonances due to quasibound states in the van der Waals wells. Although tunneling is fairly well accounted for by RPMD even below the crossover temperature, the effect of resonances, a long-time effect, is not included in the methodology. At the highest temperatures studied in this work, 2000–3300 K, the RPMD rate coefficients are somewhat larger than the QM ones, but this is shown to be due to limitations in the QM calculations and the RPMD are believed to be more reliable.