Best-of-both-worlds computational approaches to difficult-to-model dissociation reactions on metal surfaces DOI Creative Commons
Geert–Jan Kroes, Jörg Meyer

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 5, 2024

The accurate modeling of dissociative chemisorption molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant heterogeneously catalyzed reactive processes in computational catalysis. first important the field that barriers for are not yet available from principles methods. For systems prone charge transfer (for which difference between work function surface electron affinity molecule larger than 7 eV) this problem can be circumvented: chemically barrier heights extracted with a semi-empirical version density functional theory (DFT). However, second posed by (full or partial) molecule. these Born-Oppenheimer approximation breaks down, currently no method established accuracy exists resulting effect non-adiabatic energy dissipation reaction. Because two problems exist class reactions, approach computing heights, would demand computed experimental probabilities match, unlikely work. This Perspective vision how may solved. We suggest parameterized functionals used as previous DFT, but parameters based calculations electronic structure also diffusion Monte-Carlo (DMC) random phase (RPA) probably best methods pursue framework we call first-principles DFT (FPB-DFT) - providing DMC RPA steppingstone towards benchmarking future applications Probably FPB screened hybrid exchange combination non-local van der Waals correlation. propose new friction called scattering potential (SPF) could combine advantages avoid disadvantages main existing approaches describing effects: extracting calculation full molecule-metal system, it might possible compute coefficients shifts computationally convenient robust fashion. Combining FPB-DFT SPF eventually result chemical difficult-to-model transfer. should enable construction representative database surfaces. Such allow testing functionals, or, more generally, reactions huge importance industry. Additionally, sub-class focus essential sustainable chemistry future. Adding envisaged large databases already mostly addressing gas will have claim universality,

Язык: Английский

Reaction barriers at metal surfaces computed using the random phase approximation: Can we beat DFT in the generalized gradient approximation? DOI

B. Oudot,

Katharina Doblhoff-Dier

The Journal of Chemical Physics, Год журнала: 2024, Номер 161(5)

Опубликована: Авг. 2, 2024

Reaction barriers for molecules dissociating on metal surfaces (as relevant to heterogeneous catalysis) are often difficult predict accurately with density functional theory (DFT). Although the results obtained several dissociative chemisorption reactions via DFT in generalized gradient approximation (GGA), meta-GGA, and GGA exchange + van der Waals correlation scatter around true reaction barrier, there is an entire class of which GGA-type functionals collectively underestimate barrier. Little known why GGA-DFT fails some cases not others, we do know whether other methods suffer from same inconsistency. Here, present barrier heights random phase adiabatic-connection fluctuation-dissipation theorem (ACFDT-RPA) hybrid different amounts exact exchange. By comparing H2 Al(110) (where underestimates barrier) Cu(111) scatters barrier), can gauge inconsistent description systems persists ACFDT-RPA. We find improve relative two systems, but fall short chemical accuracy. ACFDT-RPA improves further leads chemically accurate both systems. Together analysis states selected GGA, functionals, these allow us discuss possible origins behavior GGA-based molecule–metal barriers.

Язык: Английский

Процитировано

4
Dissociative chemisorption of O2 on Al(111): dynamics on a potential energy surface computed with a non-self-consistent screened hybrid density functional approach DOI

Robert A. B. van Bree,

Nick Gerrits, Geert–Jan Kroes

и другие.

Faraday Discussions, Год журнала: 2024, Номер 251, С. 361 - 381

Опубликована: Янв. 1, 2024

Non-SCF hybrid DFT reaction probabilities reproduce SCF results with near-chemical accuracy; non-SCF barriers are higher. Computation time is reduced by more than an order of magnitude going from to hybrid.

Язык: Английский

Процитировано

4
Resolution of Selectivity Steps of CO Reduction Reaction on Copper by Quantum Monte Carlo DOI
Roman Fanta, Michal Bajdich

The Journal of Physical Chemistry Letters, Год журнала: 2025, Номер unknown, С. 1494 - 1500

Опубликована: Фев. 3, 2025

Electrochemical reduction of carbon monoxide to valuable fuels and chemicals on copper surfaces remains a challenging area in catalysis due limited understanding adsorption mechanisms reaction pathways. Although density functional theory (DFT)-based studies have investigated these processes, their accuracy varies across different functionals. Here, we present the application fixed-node diffusion Monte Carlo (FNDMC) benchmark energies CO*, H*, key CO (CORR) intermediates, COH* CHO* Cu(111) surface. Our results for CO* H* closely align with experimentally measured chemisorption reactions, highlighting limitations DFT providing site-specific energy comparisons that are often not available experimentally. Additionally, explore effect explicit solvation, demonstrating how water stabilizes over CHO*, thus suggesting critical role CORR. Finally, release our high-accuracy FNDMC benchmarks testing developing new functionals electrocatalysis. Overall, this study underscores potential detailed surface chemistry offers insights into catalytic processes.

Язык: Английский

Процитировано

0
Limits of BOSS DFT: O2 + Al(111) Dynamics on a Screened Hybrid Van der Waals DFT Potential Energy Surface DOI Creative Commons

Robert A. B. van Bree,

Geert–Jan Kroes

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Март 6, 2025

Язык: Английский

Процитировано

0
Capitalistic Chemistry DOI Creative Commons
Lars G. M. Pettersson

The Journal of Physical Chemistry C, Год журнала: 2025, Номер 129(11), С. 5287 - 5300

Опубликована: Март 5, 2025

The concept of "bond strength" is essence for modeling every kind reactive chemistry. Particularly within the field catalysis and surface science, interaction strength adsorbates to surfaces affects activity, selectivity, stability intermediates transition states. Here, we introduce a simple approach chemical reactions through an analogy with business. We regard rehybridization as investment molecule makes prepare its electronic geometrical structure form new bonds. resulting bond total proceeds from formation, difference (exothermicity) profit. predictive power lies in fact that any change formation requires involvement specific excited Thus, knowledge energy needed this excitation (investment) one can predict whether reaction or bonding mode will be favored. apply rationalize observed binding modes at often large structural changes even "weakly" chemisorbed systems finally justify using small metal clusters correct chemisorption energies periodic DFT calculations.

Язык: Английский

Процитировано

0
O2 Dissociation on Cu(111) Dynamics on a Novel Screened Hybrid van der Waals DFT Potential Energy Surface DOI Creative Commons

Robert A. B. van Bree,

Geert–Jan Kroes

The Journal of Physical Chemistry C, Год журнала: 2024, Номер 128(45), С. 19182 - 19196

Опубликована: Ноя. 4, 2024

The dissociative chemisorption (DC) of O2 on Cu(111) has been extensively studied by both theory and experimentation. Different experiments disagree the underlying mechanisms (direct or indirect) for sticking O2. Thus far, studies based density functional (DFT) favor indirect mechanism. However, DFT not fully resolved discussion as generalized gradient approximation (GGA) always substantially overestimated reactivity probabilities other Cu surfaces. Recent work indicated that this overestimation is due to failure GGA describe molecule–metal systems where charge transfer energy (ECT), i.e., function metal surface minus electron affinity molecule, below 7 eV. + one such system. This presents computed HSE06-1/2x-VdWDF2 screened hybrid van der Waals (DF), which applied self-consistently. A six-dimensional static potential (PES) was constructed using corrugation-reducing procedure, keeping atoms fixed. PES used perform quasi-classical trajectory calculations compute Cu(111). For first time, we present DFT-based underestimate experimental probabilities. While reproducing results would have even more desirable, fact found a DF underestimates measured means lower fraction exact exchange will most likely system with high accuracy. Furthermore, our shows evidence presence direct chemisorptions. precursor-mediated mechanism occurs low-incidence supplanted at higher incidence energies. Lastly, suggests temperature may also affect dissociation mechanism, but still needs further verification different theoretical framework allows simulation temperature.

Язык: Английский

Процитировано

2
Best-of-both-worlds computational approaches to difficult-to-model dissociation reactions on metal surfaces DOI Creative Commons
Geert–Jan Kroes, Jörg Meyer

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 5, 2024

The accurate modeling of dissociative chemisorption molecules on metal surfaces presents an exciting scientific challenge to theorists, and is practically relevant heterogeneously catalyzed reactive processes in computational catalysis. first important the field that barriers for are not yet available from principles methods. For systems prone charge transfer (for which difference between work function surface electron affinity molecule larger than 7 eV) this problem can be circumvented: chemically barrier heights extracted with a semi-empirical version density functional theory (DFT). However, second posed by (full or partial) molecule. these Born-Oppenheimer approximation breaks down, currently no method established accuracy exists resulting effect non-adiabatic energy dissipation reaction. Because two problems exist class reactions, approach computing heights, would demand computed experimental probabilities match, unlikely work. This Perspective vision how may solved. We suggest parameterized functionals used as previous DFT, but parameters based calculations electronic structure also diffusion Monte-Carlo (DMC) random phase (RPA) probably best methods pursue framework we call first-principles DFT (FPB-DFT) - providing DMC RPA steppingstone towards benchmarking future applications Probably FPB screened hybrid exchange combination non-local van der Waals correlation. propose new friction called scattering potential (SPF) could combine advantages avoid disadvantages main existing approaches describing effects: extracting calculation full molecule-metal system, it might possible compute coefficients shifts computationally convenient robust fashion. Combining FPB-DFT SPF eventually result chemical difficult-to-model transfer. should enable construction representative database surfaces. Such allow testing functionals, or, more generally, reactions huge importance industry. Additionally, sub-class focus essential sustainable chemistry future. Adding envisaged large databases already mostly addressing gas will have claim universality,

Язык: Английский

Процитировано

2