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This content will become publicly available on May 13, 2017

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

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.
 [1] ;  [1]
  1. Univ. of Massachusetts, Amherst, MA (United States)
Publication Date:
OSTI Identifier:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 18; Journal ID: ISSN 0021-9606
American Institute of Physics (AIP)
Research Org:
Univ. of Massachusetts, Amherst, MA (United States)
Sponsoring Org:
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY dissociation; methane; atom surface collisions; metal surfaces; chemisorption