A Caltech Library Service

Competing, Coverage-Dependent Decomposition Pathways for C_2H_y Species on Nickel (111)

Mueller, Jonathan E. and van Duin, Adri C. T. and Goddard, William A., III (2010) Competing, Coverage-Dependent Decomposition Pathways for C_2H_y Species on Nickel (111). Journal of Physical Chemistry C, 114 (47). pp. 20028-20041. ISSN 1932-7447.

PDF - Supplemental Material
See Usage Policy.


Use this Persistent URL to link to this item:


Competing, coverage-dependent pathways for ethane (CH_3CH_3) decomposition on Ni(111) are proposed on the basis of quantum mechanics (QM) calculations, performed by using the PBE flavor of density functional theory (DFT), for all C_2H_y species adsorbed to a periodically infinite Ni(111) surface. For CH_2CH_3, CHCH_3, and CCH_3, we find that the surface C is tetrahedral in each case, with the surface C forming bonds to one, two, or three Ni atoms with bond energies scaling nearly linearly (E_(bond) = 32.5, 82.7, and 130.8 kcal/mol, respectively). In each of the remaining six C_2H_y species, both C atoms are able to form bonds to the surface. Three of these (CH_2CH_2, CHCH_2, and CCH_2) adsorb most favorably at a fcc-top site with the methylene C located at an on-top site and the other C at an adjacent fcc site. The bond energies for these species are E_(bond) = 19.7, 63.2, and 93.6 kcal/mol, respectively. The remaining species (CHCH, CCH, and C_2) all prefer binding at fcc-hcp sites, where the C atoms sit in a pair of adjacent fcc and hcp sites, with binding energies of E_(bond) = 57.7, 120.4, and 162.8 kcal/mol, respectively. We find that CHCH_(ad) is the most stable surface species (ΔH_(eth) = −18.6), and an important intermediate along the lowest-energy decomposition pathway for ethane on Ni(111). The second most stable species, CCH_3, is a close competitor (ΔH_(eth) = −18.2 kcal/mol), lying along an alternative decomposition pathway that is preferred for high-surface-coverage conditions. The existence of these competing, low- and high-coverage decomposition pathways is consistent with the experiments. The QM results reported here were used as training data in the development of the ReaxFF reactive force field describing hydrocarbon reactions on nickel surfaces [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 4939−4949]. This has enabled Reactive dynamics studying the chemisorption and decomposition of systems far too complex for quantum mechanics. Thus we reported recently, the chemisorption and decomposition of six different hydrocarbon species on a Ni_(468) nanoparticle catalysts using this ReaxFF description [Mueller, J. E.; van Duin, A: C. T.; Goddard, W. A. J. Phys. Chem. C 2010, 114, 5675−5685].

Item Type:Article
Related URLs:
URLURL TypeDescription DOIArticle
Mueller, Jonathan E.0000-0001-8811-8799
van Duin, Adri C. T.0000-0002-3478-4945
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2010 American Chemical Society. Received: June 15, 2010; Revised Manuscript Received: October 5, 2010. Publication Date (Web): November 4, 2010. This research was supported partly by Intel Components Research and by Intel Corporate Research. This work was supported in part by the WCU program (31- 2008-000-10055-0) through the National Research Foundation of Korea.
Funding AgencyGrant Number
National Research Foundation of Korea31-2008-000-10055-0
Issue or Number:47
Record Number:CaltechAUTHORS:20101221-080727420
Persistent URL:
Official Citation:Competing, Coverage-Dependent Decomposition Pathways for C2Hy Species on Nickel (111) Jonathan E. Mueller, Adri C. T. van Duin, William A. Goddard III The Journal of Physical Chemistry C 2010 114 (47), 20028-20041
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:21463
Deposited By: Tony Diaz
Deposited On:12 Jan 2011 18:49
Last Modified:17 Nov 2020 00:56

Repository Staff Only: item control page