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(Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers

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An Erratum to this article was published on 02 November 2011

Abstract

We have developed a method for analyzing the (hyper)polarizabilities of open-shell molecular systems. This method employs the (hyper)polarizability densities based on the natural orbitals and occupation numbers, which enables us to analyze the contributions of odd electrons having various open-shell (diradical) characters. Within broken-symmetry, i.e., spin-unrestricted, single-determinant molecular orbital and density functional theory approaches, we can also remove the spin contamination effects on these quantities through spin projection. To do that, an approximate spin projected method has been elaborated and applied to the analysis of the (hyper)polarizability of multi-radical systems. As examples, typical open-shell singlet systems, 1,3-dipoles and rectangular graphene nanoflakes, are examined.

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Acknowledgments

This work was supported by Grant-in-Aid for Scientific Research (Nos. 21350011 and 20655003) and “Japan-Belgium Cooperative Program” (J091102006) from Japan Society for the Promotion of Science (JSPS), and the global COE (center of excellence) program “Global Education and Research Center for Bio-Environmental Chemistry” of Osaka University. Theoretical calculations were partly performed using Research Center for Computational Science, Okazaki, Japan. E.B. thanks the Interuniversity Attraction Pole on “Functional Supramolecular Systems” (IUAP No. P6-27) for her postdoctoral grant. This work has also been supported by the Academy Louvain (ARC “Extended-π-Conjugated Molecular Tinkertoys for Optoelectronics, and Spintronics”) and by the Belgian Government (IUAP No P06-27 “Functional Supramolecular Systems”).

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Authors and Affiliations

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

    Masayoshi Nakano, Hitoshi Fukui, Takuya Minami, Kyohei Yoneda, Yasuteru Shigeta & Ryohei Kishi

  2. Laboratoire de Chimie Théorique, Facultés Universitaires Notre-Dame de la Paix (FUNDP), rue de Bruxelles, 61, 5000, Namur, Belgium

    Benoît Champagne & Edith Botek

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

    Takashi Kubo

  4. Research Institute for Ubiquitous Energy Devices, National Institute of Advanced Industrial Science and Technology (AIST), Ikeda, Osaka, 563-8577, Japan

    Koji Ohta & Kenji Kamada

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  1. Masayoshi Nakano
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  2. Hitoshi Fukui
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Correspondence to Masayoshi Nakano.

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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.

An erratum to this article can be found at http://dx.doi.org/10.1007/s00214-011-1064-z

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Nakano, M., Fukui, H., Minami, T. et al. (Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers. Theor Chem Acc 130, 711–724 (2011). https://doi.org/10.1007/s00214-010-0871-y

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