The Operando Nature of Isobutene Adsorbed in Zeolite H‐SSZ‐13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy DOI Creative Commons
Massimo Bocus, Sander Vandenhaute, Véronique Van Speybroeck

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Oct. 31, 2024

Abstract Unraveling the nature of adsorbed olefins in zeolites is crucial to understand numerous zeolite‐catalyzed processes. A well‐grounded theoretical description critically depends on both an accurate determination potential energy surface (PES) and a reliable account entropic effects at operating conditions. Herein, we propose transfer learning approach perform random phase approximation (RPA) quality enhanced sampling molecular dynamics simulations, thereby approaching chemical accuracy exploration PES. The proposed methodology used investigate isobutene adsorption H−SSZ−13 as prototypical system estimate relative stability physisorbed olefins, carbenium ions alkoxide species (SAS) Brønsted‐acidic zeolites. We show that tert ‐butyl ion formation highly endothermic no stabilization observed compared complex within H−SSZ−13. Hence, its predicted concentration lifetime are negligible, making direct experimental observation unlikely. Yet, it remains shallow minimum free over whole considered temperature range (273–873 K), being therefore short‐lived reaction intermediate rather than transition state species.

Language: Английский

Machine learning thermodynamic perturbation theory offers accurate activation free energies at the RPA level for alkene isomerization in zeolites DOI Creative Commons
Jérôme Rey, Michaël Badawi, Dario Rocca

et al.

Catalysis Science & Technology, Journal Year: 2024, Volume and Issue: 14(18), P. 5314 - 5323

Published: Jan. 1, 2024

Thanks to Machine Learning Perturbation Theory, a combination of AIMD with RPA was made accurately predict the activation energy alkene isomerization into Brønsted acidic zeolite.

Language: Английский

Citations

3
The Operando Nature of Isobutene Adsorbed in Zeolite H‐SSZ‐13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy DOI Creative Commons
Massimo Bocus, Sander Vandenhaute, Véronique Van Speybroeck

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 64(1)

Published: Oct. 31, 2024

Abstract Unraveling the nature of adsorbed olefins in zeolites is crucial to understand numerous zeolite‐catalyzed processes. A well‐grounded theoretical description critically depends on both an accurate determination potential energy surface (PES) and a reliable account entropic effects at operating conditions. Herein, we propose transfer learning approach perform random phase approximation (RPA) quality enhanced sampling molecular dynamics simulations, thereby approaching chemical accuracy exploration PES. The proposed methodology used investigate isobutene adsorption H−SSZ−13 as prototypical system estimate relative stability physisorbed olefins, carbenium ions alkoxide species (SAS) Brønsted‐acidic zeolites. We show that tert ‐butyl ion formation highly endothermic no stabilization observed compared complex within H−SSZ−13. Hence, its predicted concentration lifetime are negligible, making direct experimental observation unlikely. Yet, it remains shallow minimum free over whole considered temperature range (273–873 K), being therefore short‐lived reaction intermediate rather than transition state species.

Language: Английский

Citations

2
Thermodynamics of the gas-phase dimerization of formic acid: Fully anharmonic finite temperature calculations at the CCSD(T) and many DFT levels DOI
Dávid Vrška, Michal Pitoňák, Tomáš Bučko

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(17)

Published: May 1, 2024

A proof-of-concept study is undertaken to demonstrate the utility of machine learning combined with thermodynamic perturbation theory (MLPT) test accuracy electronic structure methods in finite-temperature calculations. As a example, formic acid dimer chosen, which one systems included popular benchmark set S22 [Jurečka et al., Phys. Chem. 8, 1985–1993 (2006)]. Starting from explicit molecular dynamics and integration performed at PBE + D2 level, MLPT used obtain fully anharmonic dimerization free internal energies reference quality CCSD(T) level 19 different density functional approximations, including GGA, meta-GGA, non-local, hybrid functionals without dispersion corrections. Our results are shown be both qualitatively quantitatively those obtained using conventional benchmarking strategy based on fixed structures. The HSE06 identified as best performing approximate method tested, errors being 36 41 meV, respectively.

Language: Английский

Citations

0
The Operando Nature of Isobutene Adsorbed in Zeolite H‐SSZ‐13 Unraveled by Machine Learning Potentials Beyond DFT Accuracy DOI Creative Commons
Massimo Bocus, Sander Vandenhaute, Véronique Van Speybroeck

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Oct. 31, 2024

Abstract Unraveling the nature of adsorbed olefins in zeolites is crucial to understand numerous zeolite‐catalyzed processes. A well‐grounded theoretical description critically depends on both an accurate determination potential energy surface (PES) and a reliable account entropic effects at operating conditions. Herein, we propose transfer learning approach perform random phase approximation (RPA) quality enhanced sampling molecular dynamics simulations, thereby approaching chemical accuracy exploration PES. The proposed methodology used investigate isobutene adsorption H−SSZ−13 as prototypical system estimate relative stability physisorbed olefins, carbenium ions alkoxide species (SAS) Brønsted‐acidic zeolites. We show that tert ‐butyl ion formation highly endothermic no stabilization observed compared complex within H−SSZ−13. Hence, its predicted concentration lifetime are negligible, making direct experimental observation unlikely. Yet, it remains shallow minimum free over whole considered temperature range (273–873 K), being therefore short‐lived reaction intermediate rather than transition state species.

Language: Английский

Citations

0