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Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]

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Abstract

The reaction F + H2O → HF + OH is a four-atom system that provides an important benchmark for reaction dynamics. Hydrogen atom transfer at the transition state for this reaction is expected to exhibit a strong dependence on reactant vibrational excitation. In the present study, the vibrational effects are examined by photodetachment of vibrationally excited F(H2O) precursor anions using photoelectron-photofragment coincidence (PPC) spectroscopy and compared with full six-dimensional quantum dynamical calculations on ab initio potential energy surfaces. Prior to photodetachment at UV = 4.80 eV, the overtone of the ionic hydrogen bond mode in the precursor F(H2O), 2νIHB at 2885 cm−1, was excited using a tunable IR laser. Experiment and theory show that vibrational energy in the anion can be effectively carried away by the photoelectron upon a Franck–Condon photodetachment, and also show evidence for an increase of branching into the F + H2O reactant channel. The experimental results suggest a greater role for product rotational excitation than theory. Improved potential energy surfaces and longer wavepacket propagation times would be helpful to further examine the nature of the discrepancy.

Graphical abstract: Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]−

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Publication details

The article was received on 02 Aug 2017, accepted on 23 Sep 2017 and first published on 25 Sep 2017


Article type: Edge Article
DOI: 10.1039/C7SC03364H
Citation: Chem. Sci., 2017, Advance Article
  • Open access: Creative Commons BY license
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    Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]

    A. W. Ray, J. Ma, R. Otto, J. Li, H. Guo and R. E. Continetti, Chem. Sci., 2017, Advance Article , DOI: 10.1039/C7SC03364H

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