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.…
Verfasserangaben: | Thomas MullanORCiDGND, Lorenzo MaschioORCiD, Peter SaalfrankORCiDGND, Denis UsvyatORCiD |
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DOI: | https://doi.org/10.1063/5.0082805 |
ISSN: | 0021-9606 |
ISSN: | 1089-7690 |
Pubmed ID: | https://pubmed.ncbi.nlm.nih.gov/35183075 |
Titel des übergeordneten Werks (Englisch): | The journal of chemical physics : bridges a gap between journals of physics and journals of chemistr |
Untertitel (Englisch): | Diffusion of hydrogen on alpha-Al2O3 (0001) as a test case |
Verlag: | AIP Publishing |
Verlagsort: | Melville |
Publikationstyp: | Wissenschaftlicher Artikel |
Sprache: | Englisch |
Datum der Erstveröffentlichung: | 18.02.2022 |
Erscheinungsjahr: | 2022 |
Datum der Freischaltung: | 01.03.2024 |
Band: | 156 |
Ausgabe: | 7 |
Aufsatznummer: | 074109 |
Seitenanzahl: | 11 |
Fördernde Institution: | Deutsche Forschungsgemeinschaft [INST 276/714-1]; Deutsche; Forschungsgemeinschaft under Germany's Excellence Strategy [EXC; 2008/1-390540038] |
Organisationseinheiten: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
DDC-Klassifikation: | 5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften |
Peer Review: | Referiert |
Publikationsweg: | Open Access / Hybrid Open-Access |
Lizenz (Deutsch): | CC-BY - Namensnennung 4.0 International |