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      Optical gap and fundamental gap of oligoynes and carbyne

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          Abstract

          The optoelectronic properties of various carbon allotropes and nanomaterials have been well established, while the purely sp-hybridized carbyne remains synthetically inaccessible. Its properties have therefore frequently been extrapolated from those of defined oligomers. Most analyses have, however, focused on the main optical transitions in UV-Vis spectroscopy, neglecting the frequently observed weaker optical bands at significantly lower energies. Here, we report a systematic photophysical analysis as well as computations on two homologous series of oligoynes that allow us to elucidate the nature of these weaker transitions and the intrinsic photophysical properties of oligoynes. Based on these results, we reassess the estimates for both the optical and fundamental gap of carbyne to below 1.6 eV, significantly lower than previously suggested by experimental studies of oligoynes.

          Abstract

          Carbyne, a linear sp-hybridized carbon allotrope, is synthetically inaccessible and its properties are extrapolated from those of defined oligomers. Here the authors analyze weak optical bands in two series of oligoynes and reassess the optical and fundamental gap of carbyne to lower values than previously suggested.

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          Most cited references52

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          Orbital-dependent density functionals: Theory and applications

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            Continuum solvation models: A new approach to the problem of solute’s charge distribution and cavity boundaries

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              Mind the gap!

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                Author and article information

                Contributors
                dirk.guldi@fau.de
                clemence.corminboeuf@epfl.ch
                rik.tykwinski@ualberta.ca
                holger.frauenrath@epfl.ch
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                23 September 2020
                23 September 2020
                2020
                : 11
                : 4797
                Affiliations
                [1 ]GRID grid.5330.5, ISNI 0000 0001 2107 3311, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), , Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Egerlandstraße 3, ; 91058 Erlangen, Germany
                [2 ]GRID grid.5333.6, ISNI 0000000121839049, Ecole Polytechnique Fédérale de Lausanne (EPFL), Institute of Materials, , Laboratory of Macromolecular and Organic Materials, EPFL – STI – IMX – LMOM, ; MXG 037, Station 12, 1015 Lausanne, Switzerland
                [3 ]GRID grid.5333.6, ISNI 0000000121839049, Ecole Polytechnique Fédérale de Lausanne (EPFL), , Institute of Chemical Science and Engineering, Computational Molecular Design Laboratory EPFL – SB – ISIC – LCMD, BCH 5312, ; 1015 Lausanne, Switzerland
                [4 ]GRID grid.5330.5, ISNI 0000 0001 2107 3311, Department of Chemistry and Pharmacy & Interdisciplinary Center for Molecular Materials (ICMM), , Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), ; Nikolaus-Fiebiger-Straße 10, 91058 Erlangen, Germany
                [5 ]GRID grid.17089.37, Department of Chemistry, , University of Alberta, ; Edmonton, AB T6G 2G2 Canada
                [6 ]GRID grid.8534.a, ISNI 0000 0004 0478 1713, Present Address: Adolphe Merkle Institute, , University of Fribourg, ; Chemin des Verdiers 4, 1700 Fribourg, Switzerland
                [7 ]GRID grid.493090.7, ISNI 0000 0004 4910 6615, Present Address: Institute UTINAM, UMR CNRS 6213, , University of Bourgogne Franche-Comté, ; 16 Route de Gray, 25030 Besançon, France
                [8 ]Present Address: Université de Paris, ITODYS, CNRS, F-75006 Paris, France
                Author information
                http://orcid.org/0000-0002-6371-3089
                http://orcid.org/0000-0003-0146-589X
                http://orcid.org/0000-0002-8646-9365
                http://orcid.org/0000-0002-3960-1765
                http://orcid.org/0000-0001-7993-2879
                http://orcid.org/0000-0002-7645-4784
                http://orcid.org/0000-0002-1720-6991
                Article
                18496
                10.1038/s41467-020-18496-4
                7511338
                32968057
                881067da-671d-4df2-94f8-6f4245158119
                © The Author(s) 2020

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

                History
                : 28 January 2020
                : 7 August 2020
                Funding
                Funded by: FundRef https://doi.org/10.13039/100011199, EC | EC Seventh Framework Programm | FP7 Ideas: European Research Council (FP7-IDEAS-ERC - Specific Programme: "Ideas" Implementing the Seventh Framework Programme of the European Community for Research, Technological Development and Demonstration Activities (2007 to 2013));
                Award ID: ERC Grant 239831
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/501100001659, Deutsche Forschungsgemeinschaft (German Research Foundation);
                Award ID: SFB 953
                Award Recipient :
                Funded by: FundRef https://doi.org/10.13039/501100002790, Canadian Network for Research and Innovation in Machining Technology, Natural Sciences and Engineering Research Council of Canada (NSERC Canadian Network for Research and Innovation in Machining Technology);
                Funded by: FundRef https://doi.org/10.13039/501100001711, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung (Swiss National Science Foundation);
                Award ID: SNF Grant 156001
                Award Recipient :
                Categories
                Article
                Custom metadata
                © The Author(s) 2020

                Uncategorized
                optical spectroscopy,computational chemistry
                Uncategorized
                optical spectroscopy, computational chemistry

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