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A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory

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Abstract

This study examines the radical nature and spin symmetry of the ground state of the quasi-linear acene and two-dimensional periacene series. For this purpose, high-level ab initio calculations have been performed using the multireference averaged quadratic coupled cluster theory and the COLUMBUS program package. A reference space consisting of restricted and complete active spaces is taken for the π-conjugated space, correlating 16 electrons with 16 orbitals with the most pronounced open-shell character for the acenes and a complete active-space reference approach with eight electrons in eight orbitals for the periacenes. This reference space is used to construct the total configuration space by means of single and double excitations. By comparison with more extended calculations, it is shown that a focus on the π space with a 6-31G basis set is sufficient to describe the major features of the electronic character of these compounds. The present findings suggest that the ground state is a singlet for the smaller members of these series, but that for the larger ones, singlet and triplet states are quasi-degenerate. Both the acenes and periacenes exhibit significant polyradical character beyond the traditional diradical.

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Acknowledgments

This work was supported by the National Science Foundation under Project No. CHE-1213263, by the Austrian Science Fund (SFB F41, ViCoM, and Project P20893-N19), and the Robert A. Welch Foundation under Grant No. D-0005. Shawn Horn is funded by a research fellowship at Texas Tech University. Computer time at the Vienna Scientific Cluster (Project Nos. 70151 and 70376) and by the Chemistry Computational Cluster of Texas Tech University is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemistry and Biochemistry, Texas Tech University, Lubbock, TX, 79409-1061, USA

    Shawn Horn & Hans Lischka

  2. Institute for Theoretical Chemistry, University of Vienna, Waehringerstrasse 17, 1090, Vienna, Austria

    Hans Lischka

  3. Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-University, Im Neuenheimer Feld 368, 69120, Heidelberg, Germany

    Felix Plasser

  4. Institute of Advanced Simulation, Jülich Supercomputer Centre, Forschungszentrum Jülich, 52425, Jülich, Germany

    Thomas Müller

  5. Institute for Theoretical Physics, Vienna University of Technology, Wiedner Hauptstrasse 8–10, 1040, Vienna, Austria

    Florian Libisch & Joachim Burgdörfer

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  1. Shawn Horn
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  2. Felix Plasser
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Correspondence to Hans Lischka.

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Dedicated to the memory of Professor Isaiah Shavitt and published as part of the special collection of articles celebrating his many contributions.

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Horn, S., Plasser, F., Müller, T. et al. A comparison of singlet and triplet states for one- and two-dimensional graphene nanoribbons using multireference theory. Theor Chem Acc 133, 1511 (2014). https://doi.org/10.1007/s00214-014-1511-8

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