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Singlet–triplet energy gap for trimethylenemethane, oxyallyl diradical, and related species: single- and multireference computational results

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Abstract

We have investigated the through-bond exchange interactions in three non-Kekulé hydrocarbon diradicals on the basis of single- and multireference coupled cluster and related broken-symmetry (BS) methods. The singlet–triplet energy gap (S-T gap) and diradical characters for these species are evaluated. It is found that the spin contamination involved in the BS solutions is non-negligible and the approximate spin-projection method greatly improves the usual BS solutions. As for Mukherjee’s state-specific multireference coupled cluster (MkMRCC) computations, the size-consistent correction with the UHF localized natural orbitals (ULO) is useful to obtain the qualitatively correct 2J values.

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Acknowledgments

T. S. is grateful for the Research Fellowships from Japan Society for the Promotion of Science for Young Scientists (JSPS). This work has been supported by Grants-in-Aid for Scientific Research (KAKENHI) (Nos. 21550014, 19750046, 19350070) from JSPS and that on Grant-in-Aid for Scientific Research on Innovative Areas (“Coordination Programming” area 2170, No. 22108515) from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT).

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Authors and Affiliations

  1. Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan

    Toru Saito, Satomichi Nishihara, Shusuke Yamanaka, Yasutaka Kitagawa, Takashi Kawakami, Satoru Yamada, Hiroshi Isobe & Mitsutaka Okumura

  2. NanoScience Design Center, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka, 560-8531, Japan

    Kizashi Yamaguchi

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  1. Toru Saito
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  2. Satomichi Nishihara
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  3. Shusuke Yamanaka
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  4. Yasutaka Kitagawa
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Correspondence to Toru Saito.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Appendix

Definitions of acronyms are given in Table 7.

Table 7 Acronyms used in the text
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Saito, T., Nishihara, S., Yamanaka, S. et al. Singlet–triplet energy gap for trimethylenemethane, oxyallyl diradical, and related species: single- and multireference computational results. Theor Chem Acc 130, 739–748 (2011). https://doi.org/10.1007/s00214-011-0914-z

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