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Title: Communication: Fingerprints of reaction mechanisms in product distributions: Eley-Rideal-type reactions between D and CD 3/Cu(111)

Abstract

Through extensive direct dynamics studies of a prototypical Eley-Rideal type process, we demonstrate that fingerprints of microscopic reaction mechanisms can be identified in product distributions. Specifically, the umbrella vibration of CD 4 formed by reacting gaseous D atoms with CD 3 adsorbed on Cu(111) is highly excited if the reaction is initiated by a direct collision between the reactants due to the necessary inversion of the CD 3 moiety. On the other hand, an indirect collision via a hot atom mechanism leads to much lower excitation in this product vibrational mode, and as such, an inversion is unnecessary. Furthermore, this fingerprint suggests an experimentally verifiable means to disentangle different mechanistic pathways.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Univ. of Science and Technology of China, Anhui (China)
  3. Centro de Física de Materiales Centro Mixto, San Sebastian (Spain); Donostia International Physics Center DIPC, San Sebastian (Spain)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543872
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 3; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Zhou, Linsen, Jiang, Bin, Alducin, Maite, and Guo, Hua. Communication: Fingerprints of reaction mechanisms in product distributions: Eley-Rideal-type reactions between D and CD3/Cu(111). United States: N. p., 2018. Web. doi:10.1063/1.5039749.
Zhou, Linsen, Jiang, Bin, Alducin, Maite, & Guo, Hua. Communication: Fingerprints of reaction mechanisms in product distributions: Eley-Rideal-type reactions between D and CD3/Cu(111). United States. doi:10.1063/1.5039749.
Zhou, Linsen, Jiang, Bin, Alducin, Maite, and Guo, Hua. Tue . "Communication: Fingerprints of reaction mechanisms in product distributions: Eley-Rideal-type reactions between D and CD3/Cu(111)". United States. doi:10.1063/1.5039749. https://www.osti.gov/servlets/purl/1543872.
@article{osti_1543872,
title = {Communication: Fingerprints of reaction mechanisms in product distributions: Eley-Rideal-type reactions between D and CD3/Cu(111)},
author = {Zhou, Linsen and Jiang, Bin and Alducin, Maite and Guo, Hua},
abstractNote = {Through extensive direct dynamics studies of a prototypical Eley-Rideal type process, we demonstrate that fingerprints of microscopic reaction mechanisms can be identified in product distributions. Specifically, the umbrella vibration of CD4 formed by reacting gaseous D atoms with CD3 adsorbed on Cu(111) is highly excited if the reaction is initiated by a direct collision between the reactants due to the necessary inversion of the CD3 moiety. On the other hand, an indirect collision via a hot atom mechanism leads to much lower excitation in this product vibrational mode, and as such, an inversion is unnecessary. Furthermore, this fingerprint suggests an experimentally verifiable means to disentangle different mechanistic pathways.},
doi = {10.1063/1.5039749},
journal = {Journal of Chemical Physics},
number = 3,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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