skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies

Abstract

Here, mean-field microkinetic models in combination with Brønsted–Evans–Polanyi like scaling relations have proven highly successful in identifying catalyst materials with good or promising reactivity and selectivity. Analysis of the microkinetic model by means of lattice kinetic Monte Carlo promises a faithful description of a range of atomistic features involving short-range ordering of species in the vicinity of an active site. In this paper, we use the “fruit fly” example reaction of CO oxidation on fcc(111) transition and coinage metals to motivate and develop a lattice kinetic Monte Carlo solver suitable for the numerically challenging case of vastly disparate rate constants. As a result, we show that for the case of infinitely fast diffusion and absence of adsorbate-adsorbate interaction it is, in fact, possible to match the prediction of the mean-field-theory method and the lattice kinetic Monte Carlo method. As a corollary, we conclude that lattice kinetic Monte Carlo simulations of surface chemical reactions are most likely to provide additional insight over mean-field simulations if diffusion limitations or adsorbate–adsorbate interactions have a significant influence on the mixing of the adsorbates.

Authors:
ORCiD logo [1];  [1]
  1. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1457053
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 14; Journal Issue: 3; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 97 MATHEMATICS AND COMPUTING

Citation Formats

Hoffmann, Max J., and Bligaard, Thomas. A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.jctc.7b00683.
Hoffmann, Max J., & Bligaard, Thomas. A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies. United States. https://doi.org/10.1021/acs.jctc.7b00683
Hoffmann, Max J., and Bligaard, Thomas. Mon . "A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies". United States. https://doi.org/10.1021/acs.jctc.7b00683. https://www.osti.gov/servlets/purl/1457053.
@article{osti_1457053,
title = {A Lattice Kinetic Monte Carlo Solver for First-Principles Microkinetic Trend Studies},
author = {Hoffmann, Max J. and Bligaard, Thomas},
abstractNote = {Here, mean-field microkinetic models in combination with Brønsted–Evans–Polanyi like scaling relations have proven highly successful in identifying catalyst materials with good or promising reactivity and selectivity. Analysis of the microkinetic model by means of lattice kinetic Monte Carlo promises a faithful description of a range of atomistic features involving short-range ordering of species in the vicinity of an active site. In this paper, we use the “fruit fly” example reaction of CO oxidation on fcc(111) transition and coinage metals to motivate and develop a lattice kinetic Monte Carlo solver suitable for the numerically challenging case of vastly disparate rate constants. As a result, we show that for the case of infinitely fast diffusion and absence of adsorbate-adsorbate interaction it is, in fact, possible to match the prediction of the mean-field-theory method and the lattice kinetic Monte Carlo method. As a corollary, we conclude that lattice kinetic Monte Carlo simulations of surface chemical reactions are most likely to provide additional insight over mean-field simulations if diffusion limitations or adsorbate–adsorbate interactions have a significant influence on the mixing of the adsorbates.},
doi = {10.1021/acs.jctc.7b00683},
journal = {Journal of Chemical Theory and Computation},
number = 3,
volume = 14,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Steady-state detection scheme or steady-state after Rossetti. The original signal (blue) is shown together with its exponentially weighted moving average (EWMA, red). The controlled fraction (thick black line) indicates which part of the EWMA stays within the lower and upper control limit (black dashed line). Sampling of themore » kMC signal continues until less than a given fraction (e.g. 0.05) of the full trajectory is outside the control limit.« less

Save / Share:

Works referenced in this record:

New design paradigm for heterogeneous catalysts
journal, April 2015

  • Vojvodic, Aleksandra; Nørskov, Jens K.
  • National Science Review, Vol. 2, Issue 2
  • DOI: 10.1093/nsr/nwv023

Density functional theory in surface chemistry and catalysis
journal, January 2011

  • Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
  • DOI: 10.1073/pnas.1006652108

Towards the computational design of solid catalysts
journal, April 2009

  • Nørskov, J.; Bligaard, T.; Rossmeisl, J.
  • Nature Chemistry, Vol. 1, Issue 1, p. 37-46
  • DOI: 10.1038/nchem.121

Accurate coverage-dependence incorporated into first-principles kinetic models: Catalytic NO oxidation on Pt (111)
journal, February 2012


CO Oxidation on Pd(111): A First-Principles-Based Kinetic Monte Carlo Study
journal, May 2014

  • Piccinin, Simone; Stamatakis, Michail
  • ACS Catalysis, Vol. 4, Issue 7
  • DOI: 10.1021/cs500377j

Rationalizing the Relation between Adlayer Structure and Observed Kinetics in Catalysis
journal, February 2016


Adlayer inhomogeneity without lateral interactions: Rationalizing correlation effects in CO oxidation at RuO 2 (110) with first-principles kinetic Monte Carlo
journal, February 2011

  • Matera, Sebastian; Meskine, Hakim; Reuter, Karsten
  • The Journal of Chemical Physics, Vol. 134, Issue 6
  • DOI: 10.1063/1.3553258

Does phenomenological kinetics provide an adequate description of heterogeneous catalytic reactions?
journal, May 2007

  • Temel, Burcin; Meskine, Hakim; Reuter, Karsten
  • The Journal of Chemical Physics, Vol. 126, Issue 20
  • DOI: 10.1063/1.2741556

Monte Carlo and density functional theory analysis of the distribution of gold and palladium atoms on Au Pd ( 111 ) alloys
journal, January 2008


Kinetic Monte Carlo simulations of surface reactions on supported nanoparticles: A novel approach and computer code
journal, July 2015

  • Kunz, Lothar; Kuhn, Frank M.; Deutschmann, Olaf
  • The Journal of Chemical Physics, Vol. 143, Issue 4
  • DOI: 10.1063/1.4926924

A local superbasin kinetic Monte Carlo method
journal, April 2013

  • Fichthorn, Kristen A.; Lin, Yangzheng
  • The Journal of Chemical Physics, Vol. 138, Issue 16
  • DOI: 10.1063/1.4801869

Accurate acceleration of kinetic Monte Carlo simulations through the modification of rate constants
journal, May 2010

  • Chatterjee, Abhijit; Voter, Arthur F.
  • The Journal of Chemical Physics, Vol. 132, Issue 19
  • DOI: 10.1063/1.3409606

Generalized Temporal Acceleration Scheme for Kinetic Monte Carlo Simulations of Surface Catalytic Processes by Scaling the Rates of Fast Reactions
journal, March 2017

  • Dybeck, Eric C.; Plaisance, Craig P.; Neurock, Matthew
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 4
  • DOI: 10.1021/acs.jctc.6b00859

Monte Carlo Algorithms for Complex Surface Reaction Mechanisms: Efficiency and Accuracy
journal, October 2001

  • Reese, J. S.; Raimondeau, S.; Vlachos, D. G.
  • Journal of Computational Physics, Vol. 173, Issue 1
  • DOI: 10.1006/jcph.2001.6877

Efficient Exact Stochastic Simulation of Chemical Systems with Many Species and Many Channels
journal, March 2000

  • Gibson, Michael A.; Bruck, Jehoshua
  • The Journal of Physical Chemistry A, Vol. 104, Issue 9
  • DOI: 10.1021/jp993732q

Parallel kinetic Monte Carlo simulation framework incorporating accurate models of adsorbate lateral interactions
journal, December 2013

  • Nielsen, Jens; d’Avezac, Mayeul; Hetherington, James
  • The Journal of Chemical Physics, Vol. 139, Issue 22
  • DOI: 10.1063/1.4840395

An overview of spatial microscopic and accelerated kinetic Monte Carlo methods
journal, February 2007

  • Chatterjee, Abhijit; Vlachos, Dionisios G.
  • Journal of Computer-Aided Materials Design, Vol. 14, Issue 2
  • DOI: 10.1007/s10820-006-9042-9

Insights from methane decomposition on nanostructured palladium
journal, May 2016


Scaling Relations and Kinetic Monte Carlo Simulations To Bridge the Materials Gap in Heterogeneous Catalysis
journal, July 2017


Adaptive kinetic Monte Carlo for first-principles accelerated dynamics
journal, September 2008

  • Xu, Lijun; Henkelman, Graeme
  • The Journal of Chemical Physics, Vol. 129, Issue 11
  • DOI: 10.1063/1.2976010

A general method for numerically simulating the stochastic time evolution of coupled chemical reactions
journal, December 1976


A new algorithm for Monte Carlo simulation of Ising spin systems
journal, January 1975


Theoretical foundations of dynamical Monte Carlo simulations
journal, July 1991

  • Fichthorn, Kristen A.; Weinberg, W. H.
  • The Journal of Chemical Physics, Vol. 95, Issue 2
  • DOI: 10.1063/1.461138

Efficient Monte Carlo methods for the simulation of catalytic surface reactions
journal, August 1998


kmos: A lattice kinetic Monte Carlo framework
journal, July 2014

  • Hoffmann, Max J.; Matera, Sebastian; Reuter, Karsten
  • Computer Physics Communications, Vol. 185, Issue 7
  • DOI: 10.1016/j.cpc.2014.04.003

CatMAP: A Software Package for Descriptor-Based Microkinetic Mapping of Catalytic Trends
journal, February 2015


Control Chart Tests Based on Geometric Moving Averages
journal, August 1959


Trends in the Catalytic CO Oxidation Activity of Nanoparticles
journal, June 2008

  • Falsig, Hanne; Hvolbæk, Britt; Kristensen, Iben S.
  • Angewandte Chemie, Vol. 120, Issue 26
  • DOI: 10.1002/ange.200801479

    Works referencing / citing this record:

    Micro-Kinetic Modelling of CO-TPD from Fe(100)—Incorporating Lateral Interactions
    journal, March 2019

    • Gambu, Thobani; Abrahams, R.; van Steen, Eric
    • Catalysts, Vol. 9, Issue 4
    • DOI: 10.3390/catal9040310

    SQERT-T: alleviating kinetic Monte Carlo (KMC)-stiffness in transient KMC simulations
    journal, June 2018

    • Savara, Aditya; Sutton, Jonathan E.
    • Journal of Physics: Condensed Matter, Vol. 30, Issue 29
    • DOI: 10.1088/1361-648x/aacb6d

    A Practical Guide to Surface Kinetic Monte Carlo Simulations
    journal, April 2019