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Comparative study of diradical characters and third-order nonlinear optical properties of linear/cyclic acenes versus phenylenes

Authors

  • Shabbir Muhammad,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Takuya Minami,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Hitoshi Fukui,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Kyohei Yoneda,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Shu Minamide,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Ryohei Kishi,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Yasuteru Shigeta,

    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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  • Masayoshi Nakano

    Corresponding author
    1. Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
    • Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University Toyonaka, Osaka 560-8531, Japan
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Abstract

A long-range corrected spin-unrestricted density functional theory (LC-UDFT) approach has been used to investigate the diradical character (yi) and third-order nonlinear optical properties of linear/cyclic [N]acenes and [N]phenylenes in their ground states, where N is the number of benzene rings in each linear and cyclic configuration. It has been found that linear and cyclic acenes with N = 5–10 show singlet diradical characters, while linear and cyclic phenylenes with equivalent number of benzene rings have closed-shell configurations. The amplitudes of third-order nonlinear optical polarizability (γzzzz) for open-shell linear/cyclic acenes are larger especially in intermediate range of diradical character than those of closed-shell phenylene counterparts. For example, the γzzzz values of [5]cyclic acene (y0 = y1 = 0.320) is 4.89 × 103 a.u. which is about 6 times larger than those of 0.80 × 103 a.u. for closed-shell [5]cyclophenylene. Similarly, γzzzz value of [5]linear acene is also about 9 times larger than its closed-shell [5]linear phenylene counterpart. Our results show interesting insights into the relationship among the architectures, diradical characters and γzzzz values of different acenes and phenylenes. © 2012 Wiley Periodicals, Inc.

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