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Issue 3, 2019
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Uncovering the role of the stationary points in the dynamics of the F + CH3I reaction

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Abstract

We describe an analysis method which assigns geometries to stationary points along (quasi)classical trajectories. The method is applied to the F + CH3I reaction, thereby uncovering the role of the minima and transition states in the dynamics of the SN2 inversion, SN2 retention via front-side attack and double inversion, induced inversion, and proton-transfer channels. Stationary-point probability distributions, stationary-point-specific trajectory orthogonal projections, root-mean-square distance distributions, transition probability matrices, and time evolutions of the stationary points reveal long-lived front-side (F⋯ICH3) and hydrogen-bonded (F⋯HCH2I) complexes in the entrance channel and significant post-reaction ion-dipole complex (FCH3⋯I) formation in the SN2 exit channel. Most of the proton-transfer stationary points (FH⋯CH2I) participate in all the reaction channels with larger distance deviations than the double-inversion transition state. Significant forward–backward transitions are observed between the minima and transition states indicating complex, indirect dynamics. The utility of distance and energy constraints is also investigated, thereby restricting the assignment into uniform configuration or energy ranges around the stationary points.

Graphical abstract: Uncovering the role of the stationary points in the dynamics of the F− + CH3I reaction

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Publication details

The article was received on 05 Oct 2018, accepted on 20 Dec 2018 and first published on 21 Dec 2018


Article type: Paper
DOI: 10.1039/C8CP06207B
Citation: Phys. Chem. Chem. Phys., 2019,21, 1578-1586

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    Uncovering the role of the stationary points in the dynamics of the F + CH3I reaction

    B. Olasz and G. Czakó, Phys. Chem. Chem. Phys., 2019, 21, 1578
    DOI: 10.1039/C8CP06207B

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