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

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 h?UV = 4.80 eV, the overtone of the ionic hydrogen bond mode in the precursor F-(H2O), 2?IHB 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.

SUBMITTER: Ray AW 

PROVIDER: S-EPMC5674243 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature