Quasiclassical Trajectory Study of the Rotational Mode Specificity in the O(P-3) + CHD3(v(1)=0, 1, JK) -> OH + CD3 Reactions

Czakó, Gábor (2014) Quasiclassical Trajectory Study of the Rotational Mode Specificity in the O(P-3) + CHD3(v(1)=0, 1, JK) -> OH + CD3 Reactions. JOURNAL OF PHYSICAL CHEMISTRY A, 118 (50). pp. 11683-11687. ISSN 1089-5639

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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(P-3) + 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.

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