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Structural and excited-state properties of oligoacene crystals from first principles
Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, 94720, CA, United States; Department of Physics, University of California, Berkeley, 94720-7300, CA, United States.
Centre for Material Science and Nanotechnology, University of Oslo, Oslo, NO-0316, Norway.
Department of Electrical and Computer Engineering, Division of Materials Science and Engineering, Boston University, Boston, 02215, MA, United States.
Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, 94720, CA, United States; Department of Chemistry, University of California, Berkeley, 94720-7300, CA, United States.
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2016 (English)In: Physical Review B, ISSN 2469-9950, E-ISSN 2469-9969, Vol. 93, article id 115206Article in journal (Refereed)
Abstract [en]

Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excited state properties relevant for optoelectronic applications. Predicting the structure and excited state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) does not cover the long ranged vdW dispersion interactions and do not yield excited state properties. In this work we use a a combination of DFT including vdW forces -- using both nonlocal functionals and pair-wise correction methods -- together with many-body perturbation theory (MBPT) to study the geometry and excited states, respectively, of the entire set of oligoacene crystals, from benzene to hexazene. We find that vdW methods can predict lattice constants within 1 percent of the experimental measurements, on par with the previously reported accuracy of the pair-wise approximations for the same systems. We further find that the excitations energies are sensitive to the geometry, but if optimized geometries are used MBPT can yield excited state properties within a few tenths of an eV from experiments. We elucidate trends in MBPT-charge and neutral excitation energies across the acene series and discuss the role of common approximations used in MBPT.

Place, publisher, year, edition, pages
American Physical Society, 2016. Vol. 93, article id 115206
Keywords [en]
Molecular crystals, van der Waals binding, van der Waals density functional, many-body perturbation theory, structure, excited state properties
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:mau:diva-2520DOI: 10.1103/PhysRevB.93.115206ISI: 000372715400002Scopus ID: 2-s2.0-84961911767Local ID: 20537OAI: oai:DiVA.org:mau-2520DiVA, id: diva2:1399283
Available from: 2020-02-27 Created: 2020-02-27 Last updated: 2024-06-17Bibliographically approved

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