Chapter 9 Non-linear Dynamics in Catalytic Reactions

Imbihl, R.

doi:10.1016/s1573-4331(08)00009-7

Cited by 9 publications

(22 citation statements)

References 363 publications

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“…In all cases, the cluster geometry is fixed to that obtained from the PBE VASP analysis. We obtain E a CO ≈ −3.19 eV for HF, −1.98 eV for PBE (quite consistent with the VASP value), −1.89 eV for PBE0 (close to the VASP value from the similar HSE06 functional), and −1.01 eV for CR-CC (2,3). For each of these treatments, we have also determined the singlet−triplet energy splitting, ΔE T-S , for CO yielding 5.417 eV for HF, 5.905 eV for PBE, 5.894 eV for PBE0, and 6.207 eV for CR-CC (2,3).…”

Section: Key Energetics For Co Oxidationsupporting

confidence: 84%

“…We use a LANL2DZ basis set with effective core potentials (ECP) 31 for Pd, this choice being effectively utilized for other transition metal clusters, 32 and the 6-311++G(d,p) basis set 33 for CO. Various levels of theory are considered including Hartree−Fock (HF), PBE, 23 and PBE0 34 DFT functionals, and CR-CC (2,3). In all cases, the cluster geometry is fixed to that obtained from the PBE VASP analysis.…”

Section: Key Energetics For Co Oxidationmentioning

confidence: 99%

“…However, beyond reliable determination of energetics, an ultimate goal of theoretical studies is predictive description of the overall catalytic reaction kinetics and turnover frequency (TOF) often for flow reactors as a function of experimental control parameters (reactant partial pressures and surface temperature, T). 2,3 This requires molecular-level modeling of all the relevant adsorption, diffusion, desorption, and reaction processes, accounting for the diverse local environments in which they can occur. Also, such modeling must have the capability to track behavior on the appropriate time-and length-scales.…”

Section: Introductionmentioning

confidence: 99%

“…4−6 With regard to elucidation of reaction kinetics and associated assessment of steady-state bifurcation behavior in surface reactions, it should be emphasized that traditional mean-field (MF) rate equations for chemical kinetics have proved immensely valuable. 2,3,7 The prescription of rates in these equations can be guided by Langmuirian formulations for adsorption and incorporates transition-state expressions for activated processes such as desorption and reaction. Selection of activation barriers is often guided by theoretical analysis or by experiment but often incorporates an heuristic treatment of coverage dependence.…”

Section: Introductionmentioning

confidence: 99%

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Predictive Beyond-Mean-Field Rate Equations for Multisite Lattice–Gas Models of Catalytic Surface Reactions: CO Oxidation on Pd(100)

et al. 2016

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Tailored multisite lattice–gas (msLG) models are developed for CO oxidation on Pd(100) at low-pressures. These models include multiple adsorption site types and superlattice adlayer ordering due to short-range exclusion for highly mobile reactant adspecies. However, they are simplified to neglect longer-range weaker adspecies interactions, so that the key energetic parameters are the CO desorption barrier and the reaction barrier. We discuss existing density functional theory results for these energies and present additional analysis for CO adsorption. After also including an appropriate nontrivial specification of the dynamics of adsorption onto mixed reactant adlayers, we develop rate equations for the reaction kinetics. Our formulation goes beyond traditional mean-field (MF) Langmuirian treatments by accounting for multiple adsorption sites and for the strong spatial correlations associated with superlattice ordering. Specifically, we utilize factorization approximations based on appropriate site motifs, and also Padé resummation of exact low-coverage expansions for sticking coefficients. Our beyond-MF rate equations are successful in accurately predicting key aspects of reactive steady-state behavior, and thus expand the utility of rate equation formulations in surface chemistry. This is confirmed by comparison with precise kinetic Monte Carlo simulation results. Specifically, we not only assess bistability and criticality observed for CO oxidation but also find more complex multistability associated with symmetry-breaking transitions in high-coverage CO adlayers.

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Section: Key Energetics For Co Oxidationsupporting

confidence: 84%

Section: Key Energetics For Co Oxidationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Predictive Beyond-Mean-Field Rate Equations for Multisite Lattice–Gas Models of Catalytic Surface Reactions: CO Oxidation on Pd(100)

et al. 2016

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“…Thus, kinetic phase transitions and bistability [142], as well as oscillations and wave formation [143] have been observed in a variety of catalytic systems. Such phenomena have long been the focus of both experimental and theoretical studies.…”

Section: Complexity and Emergent Behaviourmentioning

confidence: 99%

Kinetic modelling of heterogeneous catalytic systems

Stamatakis

2014

J. Phys.: Condens. Matter

103

128

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The importance of heterogeneous catalysis in modern life is evidenced by the fact that numerous products and technologies routinely used nowadays involve catalysts in their synthesis or function. The discovery of catalytic materials is, however, a non-trivial procedure, requiring tedious trial-and-error experimentation. First-principles-based kinetic modelling methods have recently emerged as a promising way to understand catalytic function and aid in materials discovery. In particular, kinetic Monte Carlo (KMC) simulation is increasingly becoming more popular, as it can integrate several sources of complexity encountered in catalytic systems, and has already been used to successfully unravel the underlying physics of several systems of interest. After a short discussion of the different scales involved in catalysis, we summarize the theory behind KMC simulation, and present the latest KMC computational implementations in the field. Early achievements that transformed the way we think about catalysts are subsequently reviewed in connection to latest studies of realistic systems, in an attempt to highlight how the field has evolved over the last few decades. Present challenges and future directions and opportunities in computational catalysis are finally discussed.

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Dialectics and synergetics in chemistry. Periodic Table and oscillating reactions

Imyanitov

2015

Found Chem

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Chapter 9 Non-linear Dynamics in Catalytic Reactions

Cited by 9 publications

References 363 publications

Predictive Beyond-Mean-Field Rate Equations for Multisite Lattice–Gas Models of Catalytic Surface Reactions: CO Oxidation on Pd(100)

Predictive Beyond-Mean-Field Rate Equations for Multisite Lattice–Gas Models of Catalytic Surface Reactions: CO Oxidation on Pd(100)

Kinetic modelling of heterogeneous catalytic systems

Dialectics and synergetics in chemistry. Periodic Table and oscillating reactions

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