Rotational Mode-Specificity in the Cl + C2H6 -> HCl + C2H5 Reaction

We perform rotational mode-specific quasi-classical trajectory simulations using a high-quality ab initio analytical potential energy surface for the Cl(P-2(3/2)) + C2H6 -> HCl + C2H5 reaction. As ethane, being a prolate-type symmetric top, can be characterized by the J and K rotational quantum n...

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Bibliographic Details
Main Authors: Papp Dóra
Czakó Gábor
Format: Article
Published: 2022
Series:JOURNAL OF PHYSICAL CHEMISTRY A 126 No. 16
Subjects:
doi:10.1021/acs.jpca.2c01526

mtmt:32969450
Online Access:http://publicatio.bibl.u-szeged.hu/24764
Description
Summary:We perform rotational mode-specific quasi-classical trajectory simulations using a high-quality ab initio analytical potential energy surface for the Cl(P-2(3/2)) + C2H6 -> HCl + C2H5 reaction. As ethane, being a prolate-type symmetric top, can be characterized by the J and K rotational quantum numbers, the excitation of two rotational modes, the tumbling (J, K = 0) and spinning (J, K = J) rotations of the reactant is carried out with J = 10, 20, 30, and 40 at a wide range of collision energies. The impacts of rotational excitation on the reactivity, the mechanism, and the post-reaction distribution of energy are investigated: (1) exciting both rotational modes enhances the reactivity with the spinning rotation being more effective due to its coupling to the C-H stretching vibrational normal modes (C-H bond elongating effect) and larger rotational energies, (2) rotational excitation increases the dominance of direct rebound over the stripping mechanism, while collision energy favors the latter, (3) investing energy in tumbling rotation excites the translational motion of the products, while the excess spinning rotational energy readily flows into the internal degrees of freedom of the ethyl radical or, less significantly, into the HCl vibration, probably due to the pronounced rovibrational coupling in this case. We also study the relative efficiency of vibrational and rotational excitation on the reactivity of the barrierless and thus translationally hindered title reaction.
Physical Description:2551-2560
ISSN:1089-5639