Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals

Shoda, Jinki; Yokoyama, Masako; Yoshida, Wataru; Matsui, Hiroshi; Sugimori, Ryota; Kishi, Ryohei; Kitagawa, Yasutaka

doi:https://doi.org/10.1021/acs.jpca.4c05200

Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals

Shoda, Jinki; Yokoyama, Masako; Yoshida, Wataru et al.

Journal of Physical Chemistry A, 2024, 128(39), 8473-8482

アクセス数:54件（2025-04-27 00:17 集計）

固定URL: https://hdl.handle.net/11094/98507

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タイトル	Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals
著者	著者名 Shoda, Jinki
	著者名 Yokoyama, Masako
	著者名 Yoshida, Wataru
	NRID 1000040827284 1000040827284 著者名 Matsui, Hiroshi
	著者名 Sugimori, Ryota
	NRID 1000090452408 1000090452408 ORCID 0000-0002-6005-7629 0000-0002-6005-7629 researchmap permalink rkishi0017 rkishi0017 Scopus Author ID 7005642590 7005642590 著者名 Kishi, Ryohei
	NRID 1000060362612 1000060362612 ORCID 0000-0002-6583-7026 0000-0002-6583-7026 researchmap permalink read0068726 read0068726 Scopus Author ID 7202455934 7202455934 著者名 Kitagawa, Yasutaka
内容	Shoda J., Yokoyama M., Yoshida W., et al. Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals. Journal of Physical Chemistry A 128, 8473 (2024); https://doi.org/10.1021/acs.jpca.4c05200.
抄録	This paper theoretically investigated the correlation between the open-shell electronic structure and third-order nonlinear optical (NLO) properties of one-dimensional (1D) stacked chains of π-radicals. By employing the finite N-mer models consisting of methyl or phenalenyl radicals with different stacking distances, we evaluated the average and standard deviation of diradical characters yi for N-mer models of π-radicals (yav and ySD). Then, we estimated these diradical characters at the limit of N → ∞. These y-based indices were helpful in discussing the correlation between the open-shell electronic structures and the second hyperpolarizability per dimer at the limit N → ∞, γ∞ for the 1D chains with stacking distance alternation (SDA). The calculated γ∞ values and the polymer/dimer ratio γ∞/γ(N = 2) were enhanced significantly when both the stacking distance and SDA are small. We also found that the spin-unrestricted long-range-corrected (LC−)UBLYP method with the range-separating parameter μ = 0.47 bohr-1 well reproduced the trend of γ∞ of this type of 1D chain estimated at the spin-unrestricted coupled-cluster levels. The present study is expected to contribute to establishing the design guidelines for future high-performance open-shell molecular NLO materials.
出版者	American Chemical Society
収録物名	Journal of Physical Chemistry A
巻(号)	128(39)
ページ	8473-8482
刊行年月	2024-10-03
言語	英語
ハンドルURL	https://hdl.handle.net/11094/98507
PISSN	10895639
eISSN	15205215
関連情報 (isVersionOf)	DOI (出版社版) https://doi.org/10.1021/acs.jpca.4c05200
アクセス権	embargoed access
権利情報	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.4c05200.
権利情報	The full-text file will be made open to the public on 3 October 2025 in accordance with the publisher's policy.
出版タイプ	Accepted Manuscript
カテゴリ	学術雑誌論文 Journal Article

資源タイプ	学術雑誌論文
ローカル資源タイプ	学術雑誌論文
DCTERMS.bibliographicCitation	Journal of Physical Chemistry A. 2024, 128(39), p. 8473-8482
DC.title	Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals
DC.creator	Shoda, Jinki
	Yokoyama, Masako
	Yoshida, Wataru
	Matsui, Hiroshi
	Sugimori, Ryota
	Kishi, Ryohei
	Kitagawa, Yasutaka
DC.publisher	American Chemical Society
DC.language' scheme='DCTERMS.RFC1766	英語
DCTERMS.issued' scheme='DCTERMS.W3CDTF	2024-10-03
DC.identifier	https://doi.org/10.1021/acs.jpca.4c05200
DC.description	Shoda J., Yokoyama M., Yoshida W., et al. Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals. Journal of Physical Chemistry A 128, 8473 (2024); https://doi.org/10.1021/acs.jpca.4c05200.
DCTERMS.abstract	This paper theoretically investigated the correlation between the open-shell electronic structure and third-order nonlinear optical (NLO) properties of one-dimensional (1D) stacked chains of π-radicals. By employing the finite N-mer models consisting of methyl or phenalenyl radicals with different stacking distances, we evaluated the average and standard deviation of diradical characters yi for N-mer models of π-radicals (yav and ySD). Then, we estimated these diradical characters at the limit of N → ∞. These y-based indices were helpful in discussing the correlation between the open-shell electronic structures and the second hyperpolarizability per dimer at the limit N → ∞, γ∞ for the 1D chains with stacking distance alternation (SDA). The calculated γ∞ values and the polymer/dimer ratio γ∞/γ(N = 2) were enhanced significantly when both the stacking distance and SDA are small. We also found that the spin-unrestricted long-range-corrected (LC−)UBLYP method with the range-separating parameter μ = 0.47 bohr-1 well reproduced the trend of γ∞ of this type of 1D chain estimated at the spin-unrestricted coupled-cluster levels. The present study is expected to contribute to establishing the design guidelines for future high-performance open-shell molecular NLO materials.
DC.rights	This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.4c05200.
DC.rights	The full-text file will be made open to the public on 3 October 2025 in accordance with the publisher's policy.
DC.format	98507
citation_title	Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals
citation_author	Shoda, Jinki
	Yokoyama, Masako
	Yoshida, Wataru
	Matsui, Hiroshi
	Sugimori, Ryota
	Kishi, Ryohei
	Kitagawa, Yasutaka
citation_publisher	American Chemical Society
citation_language	英語
citation_date	2024-10-03
citation_journal_title	Journal of Physical Chemistry A
citation_volume	128
citation_issue	39
citation_firstpage	8473
citation_lastpage	8482
citation_doi	https://doi.org/10.1021/acs.jpca.4c05200
citation_public_url	https://hdl.handle.net/11094/98507

Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals

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