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Title: 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 hνUV = 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.

Authors:
 [1];  [2];  [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Univ., of California, San Diego, CA (United States)
  2. Sichuan Univ., Chengdu (China)
  3. Chongqing Univ., Chongqing (China)
  4. Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Univ., of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1506228
Grant/Contract Number:  
FG03-98ER14879
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ray, Amelia W., Ma, Jianyi, Otto, Rico, Li, Jun, Guo, Hua, and Continetti, Robert E. Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]-. United States: N. p., 2017. Web. doi:10.1039/c7sc03364h.
Ray, Amelia W., Ma, Jianyi, Otto, Rico, Li, Jun, Guo, Hua, & Continetti, Robert E. Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]-. United States. doi:10.1039/c7sc03364h.
Ray, Amelia W., Ma, Jianyi, Otto, Rico, Li, Jun, Guo, Hua, and Continetti, Robert E. Mon . "Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]-". United States. doi:10.1039/c7sc03364h. https://www.osti.gov/servlets/purl/1506228.
@article{osti_1506228,
title = {Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F–H–OH]-},
author = {Ray, Amelia W. and Ma, Jianyi and Otto, Rico and Li, Jun and Guo, Hua and Continetti, Robert E.},
abstractNote = {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 hνUV = 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.},
doi = {10.1039/c7sc03364h},
journal = {Chemical Science},
number = 11,
volume = 8,
place = {United States},
year = {2017},
month = {9}
}

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