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Reaction barriers on non-conducting surfaces beyond periodic local MP2

  • The quest for "chemical accuracy" is becoming more and more demanded in the field of structure and kinetics of molecules at solid surfaces. In this paper, as an example, we focus on the barrier for hydrogen diffusion on a alpha-Al2O3 (0001) surface, aiming for a couple cluster singles, doubles, and perturbative triples [CCSD(T)]-level benchmark. We employ the density functional theory (DFT) optimized minimum and transition state structures reported by Heiden, Usvyat, and Saalfrank [J. Phys. Chem. C 123, 6675 (2019)]. The barrier is first evaluated at the periodic Hartree-Fock and local Moller-Plesset second-order perturbation (MP2) level of theory. The possible sources of errors are then analyzed, which includes basis set incompleteness error, frozen core, density fitting, local approximation errors, as well as the MP2 method error. Using periodic and embedded fragment models, corrections to these errors are evaluated. In particular, two corrections are found to be non-negligible (both from the chemical accuracy perspective and at theThe quest for "chemical accuracy" is becoming more and more demanded in the field of structure and kinetics of molecules at solid surfaces. In this paper, as an example, we focus on the barrier for hydrogen diffusion on a alpha-Al2O3 (0001) surface, aiming for a couple cluster singles, doubles, and perturbative triples [CCSD(T)]-level benchmark. We employ the density functional theory (DFT) optimized minimum and transition state structures reported by Heiden, Usvyat, and Saalfrank [J. Phys. Chem. C 123, 6675 (2019)]. The barrier is first evaluated at the periodic Hartree-Fock and local Moller-Plesset second-order perturbation (MP2) level of theory. The possible sources of errors are then analyzed, which includes basis set incompleteness error, frozen core, density fitting, local approximation errors, as well as the MP2 method error. Using periodic and embedded fragment models, corrections to these errors are evaluated. In particular, two corrections are found to be non-negligible (both from the chemical accuracy perspective and at the scale of the barrier value of 0.72 eV): the correction to the frozen core-approximation of 0.06 eV and the CCSD(T) correction of 0.07 eV. Our correlated wave function results are compared to barriers obtained from DFT. Among the tested DFT functionals, the best performing for this barrier is B3LYP-D3.show moreshow less

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Author details:Thomas MullanORCiDGND, Lorenzo MaschioORCiD, Peter SaalfrankORCiDGND, Denis UsvyatORCiD
DOI:https://doi.org/10.1063/5.0082805
ISSN:0021-9606
ISSN:1089-7690
Pubmed ID:https://pubmed.ncbi.nlm.nih.gov/35183075
Title of parent work (English):The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr
Subtitle (English):Diffusion of hydrogen on alpha-Al2O3 (0001) as a test case
Publisher:AIP Publishing
Place of publishing:Melville
Publication type:Article
Language:English
Date of first publication:2022/02/18
Publication year:2022
Release date:2024/03/01
Volume:156
Issue:7
Article number:074109
Number of pages:11
Funding institution:Deutsche Forschungsgemeinschaft [INST 276/714-1]; Deutsche; Forschungsgemeinschaft under Germany's Excellence Strategy [EXC; 2008/1-390540038]
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
DDC classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Peer review:Referiert
Publishing method:Open Access / Hybrid Open-Access
License (German):License LogoCC-BY - Namensnennung 4.0 International
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