Rotational Mode Specificity in the F- + CH3Y [Y = F and Cl] SN2 Reactions

István Szabó, G. Czakó

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

More than 12 million quasiclassical trajectories are computed for the F- + CH3Y(v = 0, JK) [Y = F and Cl] SN2 reactions using full-dimensional ab initio analytical potential energy surfaces. The initial (J, K = 0) and (J, K = J) [J = 0, 2, 4, 6, 8] rotational state specific cross sections are obtained at different collision energies (Ecoll) in the 1-20 kcal mol-1 range, and the scattering angle and initial attack angle distributions as well as the mechanism-specific opacity functions are reported at Ecoll = 10 kcal mol-1. The tumbling rotation (K = 0) inhibits the F- + CH3F reaction by a factor of 3 for J = 8 at Ecoll = 10 kcal mol-1. This tumbling rotational effect becomes smaller at low and high Ecoll, and the tumbling motion affects the cross sections of F- + CH3Cl by only a few percent. The spinning rotation (K = J) hinders both reactions by factors in the 1.3-1.7 range for J = 8 at low Ecoll, whereas slight promotion is found as the Ecoll increases. The tumbling rotation may counteract the attractive ion-dipole forces, and the spinning motion hinders the complex formation, thereby decreasing the reactivity.

Original languageEnglish
Pages (from-to)12231-12237
Number of pages7
JournalJournal of Physical Chemistry A
Volume119
Issue number50
DOIs
Publication statusPublished - Dec 17 2015

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Barreling
metal spinning
tumbling motion
cross sections
promotion
rotational states
opacity
Potential energy surfaces
attack
Opacity
reactivity
potential energy
trajectories
dipoles
collisions
Trajectories
Scattering
Ions
scattering
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Rotational Mode Specificity in the F- + CH3Y [Y = F and Cl] SN2 Reactions. / Szabó, István; Czakó, G.

In: Journal of Physical Chemistry A, Vol. 119, No. 50, 17.12.2015, p. 12231-12237.

Research output: Contribution to journalArticle

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