Electronic structure studies and quantum scattering methods are used to elucidate the differing reactivities of methane on Ni(111) and Pt(111). For both surfaces the lowest energy pathway to dissociation is over the top site, where the static surface barrier to reaction is about 0.14 eV lower on Pt(111) than on Ni(111). If allowed to relax, both surfaces exhibit a puckering of the metal atoms in the vicinity of the adsorbates and at the transition state. Thus, motion of the lattice can change the barrier to reaction. A quantum model for dissociation is employed that includes several molecular coordinates, and allows for coupling to the lattice motion and puckering of the lattice. We find that on Ni(111) the lattice has time to pucker, increasing the reactivity relative to the static surface case. The more massive atoms on the Pt(111) surface do not have time to pucker during the reaction. As both lattices become vibrationally excited the reactivity increases significantly, particularly at low incident energies where tunneling dominates. Our model suggests that tunneling is important for these large barrier systems, particularly at the relatively low incident energies of the experiments. Our work also suggests that at the large nozzle temperatures of the experiments, there are contributions to the total reactivity from vibrationally excited molecules, particularly for Ni(111). Our model is in reasonable agreement with the experimental results for Ni(111), while we significantly underestimate the reactivity on Pt(111) as well as the difference in reactivity between Ni(111) and Pt(111). This may result from errors in our total-energy calculations and/or effects due to motion (tunneling) of the methyl group at the transition state.
Skip Nav Destination
Article navigation
7 February 2009
Research Article|
February 02 2009
Methane dissociation on Ni(111) and Pt(111): Energetic and dynamical studies
Sven Nave;
Sven Nave
a)
Department of Chemistry,
University of Massachusetts
, Amherst, Massachusetts 01003, USA
Search for other works by this author on:
Bret Jackson
Bret Jackson
b)
Department of Chemistry,
University of Massachusetts
, Amherst, Massachusetts 01003, USA
Search for other works by this author on:
a)
Electronic mail: [email protected].
b)
Electronic mail: [email protected].
J. Chem. Phys. 130, 054701 (2009)
Article history
Received:
September 18 2008
Accepted:
December 15 2008
Citation
Sven Nave, Bret Jackson; Methane dissociation on Ni(111) and Pt(111): Energetic and dynamical studies. J. Chem. Phys. 7 February 2009; 130 (5): 054701. https://doi.org/10.1063/1.3065800
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
Methane dissociation and adsorption on Ni(111), Pt(111), Ni(100), Pt(100), and Pt ( 110 ) - ( 1 × 2 ) : Energetic study
J. Chem. Phys. (February 2010)
Methane dissociation on Ni(111): The effects of lattice motion and relaxation on reactivity
J. Chem. Phys. (December 2007)
Constructing accurate potential energy surfaces for a diatomic molecule interacting with a solid surface: H 2 + Pt (111) and H 2 + Cu (100)
J. Chem. Phys. (March 2002)
The puckering free-energy surface of proline
AIP Advances (March 2013)
Quantum modelling of hydrogen chemisorption on graphene and graphite
J. Chem. Phys. (March 2014)