Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Kroes, Geert–Jan

doi:10.1039/d1cp00044f

Cited by 70 publications

(175 citation statements)

References 735 publications

(2,661 reference statements)

Supporting

Mentioning

171

Contrasting

Order By: Relevance

“…The robustness of the barrier height results to the choice of exchange correlation functionals suggests errors of this magnitude are unlikely. A recent review of the accuracy of DFT reaction barriers for reactions on surfaces leads to the conclusion that errors are typically less than about 0.2 eV [58].…”

Section: Comparison Of Experimental Results With Predictions Of Dft and The 'Standard Mechanism'mentioning

confidence: 99%

The puzzle of rapid hydrogen oxidation on Pt(111)

et al. 2021

View full text Add to dashboard Cite

We have known for over 200 years that hydrogen undergoes rapid oxidation to water on Pt catalysts; yet the reaction mechanism remains unclear. Here, we report high temporal resolution measurements of the production rate of H 2 O from hydrogen oxidation catalysed by a Pt (111) single crystal surface with a known concentration of adsorbed oxygen atoms and a step density of approximately 0.002 ML. We obtain two rate constants describing the rise, and fall of the reaction rate between 350 and 470 K and compare our observations to modern ab initio predictions of the reaction rates in surface chemistry. Remarkably, a mechanism based on a standard set of elementary reaction steps with energies and barrier heights obtained from Density Functional Theory (DFT), predicts a rate that is four orders of magnitude smaller than observed experimentally. Furthermore, the theoretically predicted reaction rate follows first-order kinetics, whereas the experimental observations clearly show a second-order reaction. The theoretical predictions are robust -six different exchange-correlation functionals lead to similar predictions. We suggest that the reason for these disagreements is that the active sites of the catalyst and the associated elementary reactions have, so far, not been properly identified.

show abstract

Section: Comparison Of Experimental Results With Predictions Of Dft and The 'Standard Mechanism'mentioning

confidence: 99%

The puzzle of rapid hydrogen oxidation on Pt(111)

et al. 2021

View full text Add to dashboard Cite

show abstract

“…However, also a hot atom-like mechanism based on a cannonball abstraction process [10,11] has been proposed. First-principles based molecular dynamics simulations including spin selection rules [12,13] have been able to reproduce and explain the experimentally observed samm sticking probability at low kinetic energies [14,15], but have not found any indications for the cannonball mechanism. On Pt(111), molecular chemisorbed O 2 molecules dissociate at higher temperatures with the oxygen atoms being preferentially to lattice sites apart from each other [8] which has also been explained by a hot atom mechanism and confirmed in kinetic Monte Carlo simulations [16].…”

Section: Introductionmentioning

confidence: 95%

“…From an experimental point of view this is due to the fact that the lifetime of dynamical hot atom events is typically so short that these events can not be directly detected. As far as simulations are concerned, in recent years significant progress has been made by performing dynamical simulations that include the coupling either to a phonon bath [15,[17][18][19][20][21] or to electron-hole pairs [22][23][24]. Such simulations have provided very valuable insights into hot atom dynamics in reactions Gambardella2001 at surfaces.…”

Section: Introductionmentioning

confidence: 99%

Hot atom chemistry: oxygen at stepped platinum surfaces

Groß

2021

Preprint

View full text Add to dashboard Cite

It is a paradigm in chemistry that chemical reaction are mainly governed by thermodynamics. Within this assumption, reaction rates can be derived from transition state theory which requires a quasi-equilibrium between reactants and activated transition state complexes that is achieved through friction. However, to reach thermal equilibrium through friction takes some time. Here we show, based on ab initio molecular dynamics simulations of the interaction of molecular oxygen with stepped Pt surfaces, that chemical reactions in heterogeneous catalysis can occur in a non-equilibrium fashion when the excess kinetic energy upon entering the potential well of a reaction intermediate is large enough.

show abstract

“…On the other hand, there has been also exciting progress in the field of surface reaction dynamics, for which we refer the readers to recent reviews. [ 6,10‐11,29‐35 ] Here, we will review recent progress of ML applications for studying gas‐surface reaction dynamics, in particular neural networks based methods. These methods allow the faithful predictions of not only energies and forces, but also other electronic properties of molecules on metal surfaces that are relevant to non‐adiabatic dynamics simulations.…”

Section: Introductionmentioning

confidence: 99%

Neural Network Representations for Studying Gas‐Surface Reaction Dynamics: Beyond the Born‐Oppenheimer Static Surface Approximation^†

et al. 2021

View full text Add to dashboard Cite

In the past a few years, there has been significant progress in theoretical characterizations of gas‐surface reaction dynamics at the atomic level. One of the major breakthroughs is the machine learning representations of the potential energy surfaces and related properties for molecules on metal surfaces from first‐principles, particularly neural networks based methods. In this review, we focus on recent advances of the development and applications of high‐dimensional symmetry‐preserving neural network representations in gas‐surface systems, which have enabled efficient Born‐Oppenheimer molecular dynamics simulations with inclusion of all molecular and surface degrees of freedom, as well as some nonadiabatic molecular dynamics simulations with effective treatment of hot electrons, at the density function theory level. Despite these advances, further challenges remain. More accurate electronic structure theories and more efficient machine learning (and active learning) algorithms are needed towards a more quantitative description of more complex gas‐surface reactions involving multiple surfaces and adsorbates or multiple electronic states.

show abstract

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Abstract: We review the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces, which is important to modeling heterogeneous catalysis for practical reasons, and...

Cited by 70 publications

References 735 publications

The puzzle of rapid hydrogen oxidation on Pt(111)

The puzzle of rapid hydrogen oxidation on Pt(111)

Hot atom chemistry: oxygen at stepped platinum surfaces

Neural Network Representations for Studying Gas‐Surface Reaction Dynamics: Beyond the Born‐Oppenheimer Static Surface Approximation^†

Contact Info

Product

Resources

About

Computational approaches to dissociative chemisorption on metals: towards chemical accuracy

Abstract: We review the state-of-the-art in the theory of dissociative chemisorption (DC) of small gas phase molecules on metal surfaces, which is important to modeling heterogeneous catalysis for practical reasons, and...

Cited by 70 publications

References 735 publications

The puzzle of rapid hydrogen oxidation on Pt(111)

The puzzle of rapid hydrogen oxidation on Pt(111)

Hot atom chemistry: oxygen at stepped platinum surfaces

Neural Network Representations for Studying Gas‐Surface Reaction Dynamics: Beyond the Born‐Oppenheimer Static Surface Approximation†

Contact Info

Product

Resources

About

Neural Network Representations for Studying Gas‐Surface Reaction Dynamics: Beyond the Born‐Oppenheimer Static Surface Approximation^†