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Collision Energy Dependence of the Competing Mechanisms of Reaction of Chlorine Atoms with Propene

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Collision Energy Dependence of the Competing Mechanisms of Reaction of Chlorine Atoms with Propene. / Cascarini, Fred; Hornung, Balazs; Quinn, Mitch S; Robertson, Patrick; Orr-Ewing, Andrew.

In: Journal of Physical Chemistry A, Vol. 123, No. 13, 04.04.2019, p. 2679-2686.

Research output: Contribution to journalArticle

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Cascarini, Fred ; Hornung, Balazs ; Quinn, Mitch S ; Robertson, Patrick ; Orr-Ewing, Andrew. / Collision Energy Dependence of the Competing Mechanisms of Reaction of Chlorine Atoms with Propene. In: Journal of Physical Chemistry A. 2019 ; Vol. 123, No. 13. pp. 2679-2686.

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@article{933010def59f44c0ac4ba8493ec511b2,
title = "Collision Energy Dependence of the Competing Mechanisms of Reaction of Chlorine Atoms with Propene",
abstract = "Quasi-classical trajectory simulations examine the reaction of Cl with propene across a range of collision energies, from 7 to 28 kJ mol-1. The majority (70{\%} at 7 kJ mol-1, 86{\%} at 14 kJ mol-1 and 93{\%} at 28 kJ mol-1) of reactive trajectories produce HCl by direct abstraction of a hydrogen atom from the methyl group of propene, but the remainder involve a variety of delayed mechanisms. Among these longer-lived trajectories, transient formation of an energized 1-chloropropyl radical intermediate is predominant, with only a minor contribution from the 2-chloropropyl radical and roaming pathways. The branching ratios between these intermediate states are largely invariant to collision energy, although the overall proportion of indirect trajectories increases at lower collision energies. The greater role for longer-lived trajectories is reflected in the computed product scattering angle distributions, which become more isotropic at lower energies. However, the distributions of population over vibrational and rotational states of the product HCl do not change with collision energy because they are controlled by the dynamics late along the reaction path.",
author = "Fred Cascarini and Balazs Hornung and Quinn, {Mitch S} and Patrick Robertson and Andrew Orr-Ewing",
note = "Special issue “Hanna Reisler Festschrift”",
year = "2019",
month = "4",
day = "4",
doi = "10.1021/acs.jpca.9b01370",
language = "English",
volume = "123",
pages = "2679--2686",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "13",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Collision Energy Dependence of the Competing Mechanisms of Reaction of Chlorine Atoms with Propene

AU - Cascarini, Fred

AU - Hornung, Balazs

AU - Quinn, Mitch S

AU - Robertson, Patrick

AU - Orr-Ewing, Andrew

N1 - Special issue “Hanna Reisler Festschrift”

PY - 2019/4/4

Y1 - 2019/4/4

N2 - Quasi-classical trajectory simulations examine the reaction of Cl with propene across a range of collision energies, from 7 to 28 kJ mol-1. The majority (70% at 7 kJ mol-1, 86% at 14 kJ mol-1 and 93% at 28 kJ mol-1) of reactive trajectories produce HCl by direct abstraction of a hydrogen atom from the methyl group of propene, but the remainder involve a variety of delayed mechanisms. Among these longer-lived trajectories, transient formation of an energized 1-chloropropyl radical intermediate is predominant, with only a minor contribution from the 2-chloropropyl radical and roaming pathways. The branching ratios between these intermediate states are largely invariant to collision energy, although the overall proportion of indirect trajectories increases at lower collision energies. The greater role for longer-lived trajectories is reflected in the computed product scattering angle distributions, which become more isotropic at lower energies. However, the distributions of population over vibrational and rotational states of the product HCl do not change with collision energy because they are controlled by the dynamics late along the reaction path.

AB - Quasi-classical trajectory simulations examine the reaction of Cl with propene across a range of collision energies, from 7 to 28 kJ mol-1. The majority (70% at 7 kJ mol-1, 86% at 14 kJ mol-1 and 93% at 28 kJ mol-1) of reactive trajectories produce HCl by direct abstraction of a hydrogen atom from the methyl group of propene, but the remainder involve a variety of delayed mechanisms. Among these longer-lived trajectories, transient formation of an energized 1-chloropropyl radical intermediate is predominant, with only a minor contribution from the 2-chloropropyl radical and roaming pathways. The branching ratios between these intermediate states are largely invariant to collision energy, although the overall proportion of indirect trajectories increases at lower collision energies. The greater role for longer-lived trajectories is reflected in the computed product scattering angle distributions, which become more isotropic at lower energies. However, the distributions of population over vibrational and rotational states of the product HCl do not change with collision energy because they are controlled by the dynamics late along the reaction path.

UR - http://www.scopus.com/inward/record.url?scp=85063375212&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.9b01370

DO - 10.1021/acs.jpca.9b01370

M3 - Article

C2 - 30865455

AN - SCOPUS:85063375212

VL - 123

SP - 2679

EP - 2686

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 13

ER -