Quasiclassical trajectory study of the rotational mode specificity in the O(3P) + CHD3(v1 = 0, 1, JK) → OH + CD3 reactions

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Abstract

Quasiclassical trajectory computations on an ab initio potential energy surface reveal that rotational excitation can significantly enhance the reactivity of the ground-state and CH stretching-excited O(3P) + CHD3(v1 = 0,1, JK) → OH + CD3 reactions. The state-specific rotational effects investigated up to J = 8 show that the K = 0 (tumbling rotation) enhancement factors can be as large as 1.5-3.5 depending on J and the collision energy, whereas the K = J (spinning rotation about the CH axis) excitations do not have any significant effect on the reactivity. The shapes of the opacity functions and scattering angle distributions depend on the initial vibrational state, but show virtually no JK dependence. The origin of the K = 0 rotational enhancements is that the tumbling rotation enlarges the range of the reactive initial attack angles, thereby increasing the reactivity. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)11683-11687
Number of pages5
JournalJournal of Physical Chemistry A
Volume118
Issue number50
DOIs
Publication statusPublished - Dec 18 2014

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Barreling
reactivity
Trajectories
trajectories
methylidyne
Potential energy surfaces
augmentation
Opacity
opacity
vibrational states
Ground state
metal spinning
attack
Stretching
excitation
potential energy
Scattering
collisions
ground state
scattering

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

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title = "Quasiclassical trajectory study of the rotational mode specificity in the O(3P) + CHD3(v1 = 0, 1, JK) → OH + CD3 reactions",
abstract = "Quasiclassical trajectory computations on an ab initio potential energy surface reveal that rotational excitation can significantly enhance the reactivity of the ground-state and CH stretching-excited O(3P) + CHD3(v1 = 0,1, JK) → OH + CD3 reactions. The state-specific rotational effects investigated up to J = 8 show that the K = 0 (tumbling rotation) enhancement factors can be as large as 1.5-3.5 depending on J and the collision energy, whereas the K = J (spinning rotation about the CH axis) excitations do not have any significant effect on the reactivity. The shapes of the opacity functions and scattering angle distributions depend on the initial vibrational state, but show virtually no JK dependence. The origin of the K = 0 rotational enhancements is that the tumbling rotation enlarges the range of the reactive initial attack angles, thereby increasing the reactivity. (Chemical Equation Presented).",
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T1 - Quasiclassical trajectory study of the rotational mode specificity in the O(3P) + CHD3(v1 = 0, 1, JK) → OH + CD3 reactions

AU - Czakó, G.

PY - 2014/12/18

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N2 - Quasiclassical trajectory computations on an ab initio potential energy surface reveal that rotational excitation can significantly enhance the reactivity of the ground-state and CH stretching-excited O(3P) + CHD3(v1 = 0,1, JK) → OH + CD3 reactions. The state-specific rotational effects investigated up to J = 8 show that the K = 0 (tumbling rotation) enhancement factors can be as large as 1.5-3.5 depending on J and the collision energy, whereas the K = J (spinning rotation about the CH axis) excitations do not have any significant effect on the reactivity. The shapes of the opacity functions and scattering angle distributions depend on the initial vibrational state, but show virtually no JK dependence. The origin of the K = 0 rotational enhancements is that the tumbling rotation enlarges the range of the reactive initial attack angles, thereby increasing the reactivity. (Chemical Equation Presented).

AB - Quasiclassical trajectory computations on an ab initio potential energy surface reveal that rotational excitation can significantly enhance the reactivity of the ground-state and CH stretching-excited O(3P) + CHD3(v1 = 0,1, JK) → OH + CD3 reactions. The state-specific rotational effects investigated up to J = 8 show that the K = 0 (tumbling rotation) enhancement factors can be as large as 1.5-3.5 depending on J and the collision energy, whereas the K = J (spinning rotation about the CH axis) excitations do not have any significant effect on the reactivity. The shapes of the opacity functions and scattering angle distributions depend on the initial vibrational state, but show virtually no JK dependence. The origin of the K = 0 rotational enhancements is that the tumbling rotation enlarges the range of the reactive initial attack angles, thereby increasing the reactivity. (Chemical Equation Presented).

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