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HAB79: A new molecular dataset for benchmarking DFT and DFTB electronic couplings against high-level ab initio calculations

Ziogos, Orestis George; Kubas, Adam; Futera, Zdenek; Xie, Weiwei; Elstner, Marcus; Blumberger, Jochen


A new molecular dataset called HAB79 is introduced to provide ab initio reference values for electronic couplings (transfer integrals) and to benchmark density functional theory (DFT) and density functional tight-binding (DFTB) calculations. The HAB79 dataset is composed of 79 planar heterocyclic polyaromatic hydrocarbon molecules frequently encountered in organic (opto)electronics, arranged to 921 structurally diverse dimer configurations. We show that CASSCF/NEVPT2 with a minimal active space provides a robust reference method that can be applied to the relatively large molecules of the dataset. Electronic couplings are largest for cofacial dimers, in particular, sulfur-containing polyaromatic hydrocarbons, with values in excess of 0.5 eV, followed by parallel displaced cofacial dimers. V-shaped dimer motifs, often encountered in the herringbone layers of organic crystals, exhibit medium-sized couplings, whereas T-shaped dimers have the lowest couplings. DFT values obtained from the projector operator-based diabatization (POD) method are initially benchmarked against the smaller databases HAB11 (HAB7-) and found to systematically improve when climbing Jacob’s ladder, giving mean relative unsigned errors (MRUEs) of 27.7% (26.3%) for the generalized gradient approximation (GGA) functional BLYP, 20.7% (15.8%) for hybrid functional B3LYP, and 5.2% (7.5%) for the long-range corrected hybrid functional omega-B97X. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000141882
Veröffentlicht am 16.01.2022
DOI: 10.1063/5.0076010
Zitationen: 8
Web of Science
Zitationen: 11
Zitationen: 13
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Physikalische Chemie (IPC)
Publikationstyp Zeitschriftenaufsatz
Publikationsdatum 21.12.2021
Sprache Englisch
Identifikator ISSN: 0021-9606, 1089-7690, 1520-9032
KITopen-ID: 1000141882
Erschienen in Journal of Chemical Physics
Verlag American Institute of Physics (AIP)
Band 155
Heft 23
Seiten Art.-Nr. 234115
Nachgewiesen in Dimensions
Web of Science
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