Modeling surface kinetics with first-principles-based molecular simulation

Eric W. Hansen, Matthew Neurock

Research output: Contribution to journalConference articlepeer-review

75 Scopus citations


A first-principles-based dynamic Monte Carlo (MC) algorithm was developed to simulate catalytic kinetics on well-defined transition metal surface. Density functional quantum chemical calculations along with fundamental experimental data were used to establish an intrinsic kinetic database. Both pairwise and bond order conservation models were parameterized from this database and used internally in the MC simulation to describe adsorbate lateral interactions. The MC algorithm is an object-oriented simulation that tracks the dynamic changes in the atomic surface structure with changes in processing conditions by following the molecular kinetics. The MC algorithm is applied herein to two relevant catalytic systems: (1) nitric oxide decomposition on Rh (1 0 0) and (2) ethylene hydrogenation over Pd(1 0 0). The results indicate that the ab initio modified bond order conservation model provides reliable predictions of surface kinetics. The simulated temperature programmed desorption profiles agree with the experimental measurements for both NO and ethylene. The simulated overall activation energy for the kinetics of ethylene hydrogenation was 9.2 kcal/mol that compares very well with experimental estimates of 6.5-10.7 kcal/mol.

Original languageEnglish (US)
Pages (from-to)3411-3421
Number of pages11
JournalChemical Engineering Science
Issue number15-16
StatePublished - Jul 1999
EventProceedings of the 1998 15th International Symposium on Chemical Reaction Engineering, ISCRE 15 - Newport Beach, CA, USA
Duration: Sep 13 1998Sep 16 1998

Bibliographical note

Funding Information:
The authors wish to thank Professor Robert J. Davis (University of Virginia) for his helpful technical advice as well as the "nancial support of the National Science Foundation CAREER Award (CTS-9702762).


  • BOC
  • Catalysis
  • DFT
  • Ethylene hydrogenation
  • Monte Carlo
  • NO decomposition

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