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Quantum Roaming in the Complex-Forming Mechanism of the Reactions of OH with Formaldehyde and Methanol at Low Temperature and Zero Pressure: A Ring Polymer Molecular Dynamics Approach

AuthorsMazo-Sevillano, Pablo del; Aguado, Alfredo ; Jimenez, Elena; Suleimanov, Yury V.; Roncero, Octavio
Issue Date2-Apr-2019
PublisherAmerican Chemical Society
CitationJournal of Physical Chemistry Letters 10: 1900-1907 (2019)
AbstractThe quantum dynamics of the title reactions are studied using the ring polymer molecular dynamics (RPMD) method from 20 to 1200 K using recently proposed full dimensional potential energy surfaces which include long-range dipole-dipole interactions. A V-shaped dependence of the reaction rate constants is found with a minimum at 200-300 K, in rather good agreement with the current experimental data. For temperatures above 300 K the reaction proceeds following a direct H-abstraction mechanism. However, below 100 K the reaction proceeds via organic-molecule···OH collision complexes, with very long lifetimes, longer than 10 s, associated with quantum roaming arising from the inclusion of quantum effects by the use of RPMD. The long lifetimes of these complexes are comparable to the time scale of the tunnelling to form reaction products. These complexes are formed at zero pressure because of quantum effects and not only at high pressure as suggested by transition state theory (TST) calculations for OH + methanol and other OH reactions. The zero-pressure rate constants reproduce quite well measured ones below 200 K, and this agreement opens the question of how important the pressure effects on the reaction rate constants are, as implied in TST-like formalisms. The zero-pressure mechanism is applicable only to very low gas density environments, such as the interstellar medium, which are not repeatable by experiments.
Description8 pags., 5 figs., 1 tab.
Publisher version (URL)http://dx.doi.org/10.1021/acs.jpclett.9b00555
Identifiersdoi: 10.1021/acs.jpclett.9b00555
issn: 1948-7185
Appears in Collections:(CFMAC-IFF) Artículos
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