Toward Computing Accurate Free Energies in Heterogeneous Catalysis: a Case Study for Adsorbed Isobutene in H-ZSM-5.
Journal
ACS physical chemistry Au
ISSN: 2694-2445
Titre abrégé: ACS Phys Chem Au
Pays: United States
ID NLM: 9918300980006676
Informations de publication
Date de publication:
28 Sep 2022
28 Sep 2022
Historique:
entrez:
1
3
2023
pubmed:
2
3
2023
medline:
2
3
2023
Statut:
epublish
Résumé
Herein, we propose a novel computational protocol that enables calculating free energies with improved accuracy by combining the best available techniques for enthalpy and entropy calculation. While the entropy is described by enhanced sampling molecular dynamics techniques, the energy is calculated using ab initio methods. We apply the method to assess the stability of isobutene adsorption intermediates in the zeolite H-SSZ-13, a prototypical problem that is computationally extremely challenging in terms of calculating enthalpy and entropy. We find that at typical operating conditions for zeolite catalysis (400 °C), the physisorbed π-complex, and not the tertiary carbenium ion as often reported, is the most stable intermediate. This method paves the way for sampling-based techniques to calculate the accurate free energies in a broad range of chemistry-related disciplines, thus presenting a big step forward toward predictive modeling.
Identifiants
pubmed: 36855690
doi: 10.1021/acsphyschemau.2c00020
pmc: PMC9955322
doi:
Types de publication
Journal Article
Langues
eng
Pagination
399-406Informations de copyright
© 2022 The Authors. Published by American Chemical Society.
Déclaration de conflit d'intérêts
The authors declare no competing financial interest.
Références
Phys Chem Chem Phys. 2006 Sep 14;8(34):3955-65
pubmed: 17028686
Phys Rev B Condens Matter. 1996 Jul 15;54(3):1703-1710
pubmed: 9986014
Phys Rev B Condens Matter. 1993 Jan 1;47(1):558-561
pubmed: 10004490
J Phys Chem Lett. 2019 Jul 5;10(13):3727-3731
pubmed: 31244270
Angew Chem Int Ed Engl. 2014 Aug 11;53(33):8621-6
pubmed: 25065600
Phys Rev B Condens Matter. 1996 Oct 15;54(16):11169-11186
pubmed: 9984901
Acc Chem Res. 2019 Dec 17;52(12):3502-3510
pubmed: 31765121
Proc Natl Acad Sci U S A. 2017 May 16;114(20):E3900-E3908
pubmed: 28461504
J Chem Theory Comput. 2020 Oct 13;16(10):6049-6060
pubmed: 32786917
J Am Chem Soc. 2017 Jun 28;139(25):8646-8652
pubmed: 28585829
J Chem Theory Comput. 2011 Apr 12;7(4):1090-101
pubmed: 26606357
Nature. 2013 Jan 17;493(7432):365-70
pubmed: 23254929
Phys Rev B Condens Matter. 1994 May 15;49(20):14251-14269
pubmed: 10010505
J Comput Chem. 2008 Oct;29(13):2113-24
pubmed: 18473323
J Chem Phys. 2006 Jun 21;124(23):234106
pubmed: 16821906
Science. 2014 Jul 11;345(6193):197-200
pubmed: 25013071
Nat Chem. 2017 Oct;9(10):1019-1024
pubmed: 28937667
J Phys Chem Lett. 2020 Jun 4;11(11):4305-4310
pubmed: 32412766
Phys Rev Lett. 2009 Jul 31;103(5):056401
pubmed: 19792517
J Chem Phys. 2010 Apr 21;132(15):154104
pubmed: 20423165
Phys Rev Lett. 2018 Nov 9;121(19):195701
pubmed: 30468598
J Chem Theory Comput. 2021 Feb 9;17(2):1155-1169
pubmed: 33482059
Angew Chem Int Ed Engl. 2015 Jul 20;54(30):8783-6
pubmed: 26096840
Chem Soc Rev. 2015 Oct 21;44(20):7044-111
pubmed: 25976164
J Chem Theory Comput. 2021 Sep 14;17(9):5849-5862
pubmed: 34459582
J Chem Phys. 2005 Oct 8;123(14):144104
pubmed: 16238371
Angew Chem Int Ed Engl. 2016 Apr 18;55(17):5235-7
pubmed: 27008460
Phys Rev B Condens Matter. 1994 Dec 15;50(24):17953-17979
pubmed: 9976227
Angew Chem Int Ed Engl. 2010 Jun 21;49(27):4678-80
pubmed: 20491099
Chem Soc Rev. 2018 Nov 12;47(22):8307-8348
pubmed: 30204184
J Chem Phys. 2010 Apr 28;132(16):164117
pubmed: 20441268
Acc Chem Res. 2008 Aug;41(8):895-904
pubmed: 18605741
J Am Chem Soc. 2004 Mar 17;126(10):3300-9
pubmed: 15012161