Selective hydrogen production at Pt(111) investigated by Quantum Monte Carlo methods for metal catalysis

Sharma, Rajesh O.; Rantala, Tapio T.; Hoggan, Philip E.

doi:10.1002/qua.26198

Cited by 7 publications

(5 citation statements)

References 12 publications

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“…For details of computational results, see the Supporting Information and also the /figshare.com/articles/dataset. 1,15 Platinum has a 5d 9 6s 1 ground state. Because all-electron calculations are inaccessible, a Pt-atom is represented by 18 valence electrons with a suitable PP.…”

Section: ■ Computational Methodsmentioning

confidence: 99%

“…For details of computational results, see the Supporting Information and also the /figshare.com/articles/dataset. , …”

Section: Computational Methodsmentioning

confidence: 99%

“…The first step in the water−gas shift reaction on platinum is water addition to preadsorbed carbon monoxide. This takes place at the Pt(111) face 1 ultimately producing H 2 as a clean, sustainable fuel. In the present work, we evaluate the activation barrier for this water addition, to showcase the accuracy of QMC.…”

Section: ■ Introductionmentioning

confidence: 99%

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Quantum Monte Carlo Approach for Determining the Activation Barrier of Water Addition to Carbon Monoxide Adsorbed on Pt(111) within 1 kJ/mol

2020

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Quantum Monte Carlo (QMC) methods offer ab initio calculations of remarkable accuracy for reaction activation barriers (to 1 kJ/mol or 0.01 eV), even at solid surfaces. Chemical reactions generally involve bond dissociation that is poorly described by Hartree–Fock and density functional theory (DFT) methods. However, such processes are often the key to rate-limiting reaction steps at solid surfaces. In this work, a novel QMC methodology is demonstrated as a solution. Carbon monoxide (CO) on platinum reacts with water, first giving the addition products. QMC methods are used here to investigate addition at close-packed Pt(111). The CO is preadsorbed on Pt(111). First, an approaching water molecule is only partially dissociated. At the same time, its oxygen atom binds to CO giving an adsorbed formate moiety (COOH) and Pt–H. This concerted addition is rate-limiting. The QMC activation barrier (in kJ/mol) is 71.0 ± 0.7, and its apparent measured value is 71.4. This showcases QMC as a method to investigate related catalytic systems.

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Section: ■ Computational Methodsmentioning

confidence: 99%

“…For details of computational results, see the Supporting Information and also the /figshare.com/articles/dataset. , …”

Section: Computational Methodsmentioning

confidence: 99%

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Quantum Monte Carlo Approach for Determining the Activation Barrier of Water Addition to Carbon Monoxide Adsorbed on Pt(111) within 1 kJ/mol

2020

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“…Diffusion Monte Carlo (DMC) captures dispersion interactions, describes metals correctly, and has been used to describe adsorption energies as well as reaction barriers for molecules on transition metal surfaces. − DMC can be very accurate, with the potential to have errors smaller than “chemical accuracy” of 1 kcal/mol. Recent advances to automate convergence of statistical errors, , and to mitigate finite size errors that are particularly important for metallic systems, , bring DMC closer to being a widespread option for chemistry at metallic surfaces.…”

Section: Electronic Structure Accuracymentioning

confidence: 99%

Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

2022

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Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic configurations, from the extremes of classical molecular dynamics of a complete interface with point-charge atoms to correlated electronic structure methods of a single electrode configuration with no dynamics or electrolyte. Here, we review the spectrum of simulation techniques suitable for electrochemistry, focusing on the key approximations and accuracy considerations for each technique. We discuss promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient beyond density functional theory (DFT) electronic methods, that will push electrochemical simulations beyond the present frontier.

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“…Since bond dissociation and formation are both involved in this crucial step, it was previously studied by us by quite time-consuming QMC, using high-level Multi-Reference Configuration Interaction (MRCI) wave-functions as input for a molecular active site embedded in the periodic metal-catalyst lattice [1,4]. In the present study, our objective is to ascertain how well this wave-function quality can be approached using a correlated ground-state.…”

Section: Introductionmentioning

confidence: 99%

Quantum Monte Carlo with ground-state input to investigate methane reactions on supported metal film catalysts

Hoggan¹

2021

Preprint

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Nowadays, there is pressing demand for sustainable energy sources, or clean and 'green' fuel and hydrogen is a perfect candidate.This work shows how to use Quantum Monte Carlo calculations to take (user-guided) information summarising chemistry of heterogeneous catalysis from a generic Jastrow factor, that allows electron correlation to be included in the density. This, in turn, gives accurate values of properties, in particular the activation barrier for the water addition step in the catalysed water-gas shift reaction, to produce hydrogen. This step follows adsorption of CO on Pt(111), pure or layered onto the close-packed face of aluminium.The CO co-ordinates to a hollow site defined by three Pt atoms and, new to this work, an Al-atom co-ordinates the H-atom from dissociating an in-coming water molecule.This work is dedicated to the memory of Sir John Meurig Thomas 15.12.1932-13.11.2020, a great mentor in heterogeneous catalysis.The author still recalls JMT's courses with admiration and his lecture notes are a real treasure.

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Selective hydrogen production at Pt(111) investigated by Quantum Monte Carlo methods for metal catalysis

Cited by 7 publications

References 12 publications

Quantum Monte Carlo Approach for Determining the Activation Barrier of Water Addition to Carbon Monoxide Adsorbed on Pt(111) within 1 kJ/mol

Quantum Monte Carlo Approach for Determining the Activation Barrier of Water Addition to Carbon Monoxide Adsorbed on Pt(111) within 1 kJ/mol

Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Quantum Monte Carlo with ground-state input to investigate methane reactions on supported metal film catalysts

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