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Title: Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)

Abstract

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
Research Org.:
Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1253764
Alternate Identifier(s):
OSTI ID: 1253070
Grant/Contract Number:  
FG02-87ER13744
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 18; 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; dissociation; methane; atom surface collisions; metal surfaces; chemisorption

Citation Formats

Guo, Han, and Jackson, Bret. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111). United States: N. p., 2016. Web. doi:10.1063/1.4948941.
Guo, Han, & Jackson, Bret. Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111). United States. https://doi.org/10.1063/1.4948941
Guo, Han, and Jackson, Bret. Fri . "Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)". United States. https://doi.org/10.1063/1.4948941. https://www.osti.gov/servlets/purl/1253764.
@article{osti_1253764,
title = {Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH4 on Pt(111)},
author = {Guo, Han and Jackson, Bret},
abstractNote = {A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH4 dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v3 and 2v3, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v1 symmetric stretch of CH4 is more effective at promoting the dissociative chemisorption of CH4 than exciting the 1v3 antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v3 state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. As a result, our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.},
doi = {10.1063/1.4948941},
journal = {Journal of Chemical Physics},
number = 18,
volume = 144,
place = {United States},
year = {Fri May 13 00:00:00 EDT 2016},
month = {Fri May 13 00:00:00 EDT 2016}
}

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