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Issue 44, 2016
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Energetics and transition-state dynamics of the F + HOCH3 → HF + OCH3 reaction

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Abstract

The F + HOCH3 → HF + OCH3 reaction is a system with 15 internal degrees of freedom that can provide a benchmark for the development of theory for increasingly complex chemical reactions. The dynamics of this reaction were studied by photoelectron–photofragment coincidence (PPC) spectroscopy carried out on the F(HOCH3) anion, aided by a computational study of both the anion and neutral potential energy surfaces, with energies extrapolated to the CCSDT(Q)/CBS level of theory. Photodetachment at 4.80 eV accesses both the reactant and product channels for this reaction. In the product channel (HF + OCH3 + e) of the neutral potential energy surface, vibrationally excited HF products in addition to the stable product-channel hydrogen-bonded complex (FH–OCH3) are observed in the PPC and photoelectron spectra. In addition, experimental evidence is observed for the reactant-channel van der Waals complex (F–HOCH3), in good agreement with the theoretical predictions. The relative stability of these long-lived complexes was probed by reducing the ion beam energy, increasing the product time-of-flight, indicating lifetimes on the microsecond timescale for the reactant- and product-channel complexes as well as providing evidence for long-lived vibrational Feshbach resonances associated with the HF(v > 0) + OCH3 product states. This system will provide a model for extending full-dimensionality quantum dynamics to larger numbers of degrees of freedom.

Graphical abstract: Energetics and transition-state dynamics of the F + HOCH3 → HF + OCH3 reaction

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Publication details

The article was received on 16 Sep 2016, accepted on 20 Oct 2016 and first published on 21 Oct 2016


Article type: Paper
DOI: 10.1039/C6CP06409D
Citation: Phys. Chem. Chem. Phys., 2016,18, 30612-30621
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    Energetics and transition-state dynamics of the F + HOCH3 → HF + OCH3 reaction

    A. W. Ray, J. Agarwal, B. B. Shen, H. F. Schaefer and R. E. Continetti, Phys. Chem. Chem. Phys., 2016, 18, 30612
    DOI: 10.1039/C6CP06409D

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