The nonadiabatic dynamics of the reactive quenching channel of the OH(A2 sigma+) + H2/D2 collisions is investigated with a semiclassical surface hopping method, using a recently developed four-state diabatic potential energy matrix (DPEM). In agreement with experimental observations, the H2O/HOD products are found to have significant vibrational excitation. Using a Gaussian binning method, the H2O vibrational state distribution is determined. The preferential energy disposal into the product vibrational modes is rationalized by an extended Sudden Vector Projection model, in which the h and g vectors associated with the conical intersection are found to have large projections with the product normal modes. However, our calculations did not find significant insertion trajectories, suggesting the need for further improvement of the DPEM.

Nonadiabatic Reactive Quenching of OH(A2Σ+) by H2: Origin of High Vibrational Excitation in the H2O Product / S. Han, B. Zhao, R. Conte, C.L. Malbon, J.M. Bowman, D.R. Yarkony, H. Guo. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - 126:39(2022 Oct 06), pp. 6944-6952. [10.1021/acs.jpca.2c05704]

Nonadiabatic Reactive Quenching of OH(A2Σ+) by H2: Origin of High Vibrational Excitation in the H2O Product

R. Conte;
2022

Abstract

The nonadiabatic dynamics of the reactive quenching channel of the OH(A2 sigma+) + H2/D2 collisions is investigated with a semiclassical surface hopping method, using a recently developed four-state diabatic potential energy matrix (DPEM). In agreement with experimental observations, the H2O/HOD products are found to have significant vibrational excitation. Using a Gaussian binning method, the H2O vibrational state distribution is determined. The preferential energy disposal into the product vibrational modes is rationalized by an extended Sudden Vector Projection model, in which the h and g vectors associated with the conical intersection are found to have large projections with the product normal modes. However, our calculations did not find significant insertion trajectories, suggesting the need for further improvement of the DPEM.
Settore CHIM/02 - Chimica Fisica
PSRL220LPRAT_01 - Piano di Sostegno alla Ricerca 2015-2017 - Linea 2 "Dotazione annuale per attività istituzionali" (anno 2020) - PRATI, LAURA - PSR_LINEA2_ / Piano di sviluppo di ricerca - Dotazioni dipartimentali - Linea 2 - 2020
22-set-2022
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/944216
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