Theoretical Study on Third-Order Nonlinear Optical Property of One-Dimensional Cyclic Thiazyl Radical Aggregates: Intermolecular Distance, Open-Shell Nature, and Spin State Dependences

Matsui, Hiroshi;Yamane, Masaki;Tonami, Takayoshi;Nakano, Masayoshi;Champagne, Benoît;et.al.
(2018) The Journal of Physical Chemistry C — Vol. 122, n° 12, p. 6779-6785 (2018)

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  • Matsui, Hiroshiorcid-logoDepartment of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Yamane, MasakiDepartment of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Tonami, TakayoshiDepartment of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • Nakano, Masayoshiorcid-logoCenter for Spintronics Research Network (CSRN), Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531, Japan
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  • de Wergifosse, Marcorcid-logoUCLouvain
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  • Champagne, Benoîtorcid-logoLaboratoire de Chimie Théorique, Namur Institute of Structured Matter (NISM), University of Namur, rue de Bruxelles, 61, B-5000 Namur, Belgium
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Abstract
Using the spin-unrestricted density functional theory method, we investigate the relationship between structure, spin state, and second hyperpolarizability (γ) of the finite and infinite one-dimensional open-shell aggregates composed of cyclic thiazyl radicals, that is, 1,2,3,5-dithiadiazolyl (DTDA) radicals. The DTDA aggregates with antiferromagnetic spin-alignment exhibit much greater enhancement of γ than the aggregates with ferromagnetic spinalignment and the closed-shell benzene aggregates due to the intermediate open-shell singlet nature of the antiferromagnetic DTDA aggregate. It is found that this enhancement shows strong intermolecular distance dependences: the intermolecular distance giving the largest enhancement of γ decreases with increasing the number of molecules, and intermolecular distance alternation reduces the γ. For the infinite antiferromagnetic DTDA aggregate with a realistic intermolecular distance d = 3.1 Å, the γ per monomer reaches 1.9 × 106 au, which is comparable to that of the infinite open-shell singlet aggregate of phenalenyl radicals, and exhibits ∼2400 times enhancement as compared to that of the closed-shell benzene aggregate. This feature indicates the high-potential application of open-shell singlet cyclic thiazyl radical aggregates to outstanding third-order NLO materials.
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Matsui, H., Yamane, M., Tonami, T., Nakano, M., de Wergifosse, M., Seidler, T., & Champagne, B. (2018). Theoretical Study on Third-Order Nonlinear Optical Property of One-Dimensional Cyclic Thiazyl Radical Aggregates: Intermolecular Distance, Open-Shell Nature, and Spin State Dependences. The Journal of Physical Chemistry C, 122(12), 6779-6785. https://doi.org/10.1021/acs.jpcc.7b11319 (Original work published 2018)