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Title: The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study

Abstract

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO 2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO 2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO 2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1344088
Grant/Contract Number:  
FG02-87ER13744
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 7; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Farjamnia, Azar, and Jackson, Bret. The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study. United States: N. p., 2017. Web. doi:10.1063/1.4976132.
Farjamnia, Azar, & Jackson, Bret. The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study. United States. doi:10.1063/1.4976132.
Farjamnia, Azar, and Jackson, Bret. Tue . "The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study". United States. doi:10.1063/1.4976132. https://www.osti.gov/servlets/purl/1344088.
@article{osti_1344088,
title = {The dissociative chemisorption of CO 2 on Ni(100): A quantum dynamics study},
author = {Farjamnia, Azar and Jackson, Bret},
abstractNote = {A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of CO2 on Ni(100). The largest barrier to reaction corresponds to the formation of a bent anionic molecular precursor, bound to the surface by about 0.24 eV. The barrier to dissociation from this state is small. In our computed dissociative sticking probabilities on Ni(100) for molecules, the ground states are in very good agreement with available experimental data, reasonably reproducing the variation in reactivity with collision energy. Vibrational excitation of the incident CO2 can enhance reactivity, particularly for incident energies at or below threshold, and there is clear mode specific behavior. Both the vibrational enhancement and the increase in dissociative sticking with surface temperature are much weaker than that found in recent studies of methane and water dissociative chemisorption. The energetics for CO2 adsorption and dissociation on the stepped Ni(711) surface are found to be similar to that on Ni(100), except that the barrier to dissociation from the anionic precursor is even smaller on Ni(711). Here, we predict that the dissociative sticking behavior is similar on the two surfaces.},
doi = {10.1063/1.4976132},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 7,
volume = 146,
place = {United States},
year = {2017},
month = {2}
}

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