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

Number of Access:737（2025-08-14 12:35 Counts）

Identifier to cite or link to this item: https://hdl.handle.net/11094/98507

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Title	Theoretical Study on the Correlation between Open-Shell Electronic Structures and Third-Order Nonlinear Optical Properties in One-Dimensional Chains of π-Radicals
Creator	CreatorName Shoda, Jinki
	CreatorName Yokoyama, Masako
	CreatorName Yoshida, Wataru
	NRID 1000040827284 1000040827284 CreatorName Matsui, Hiroshi
	CreatorName Sugimori, Ryota
	NRID 1000090452408 1000090452408 ORCID 0000-0002-6005-7629 0000-0002-6005-7629 researchmap permalink rkishi0017 rkishi0017 Scopus Author ID 7005642590 7005642590 CreatorName Kishi, Ryohei
	NRID 1000060362612 1000060362612 ORCID 0000-0002-6583-7026 0000-0002-6583-7026 researchmap permalink read0068726 read0068726 Scopus Author ID 7202455934 7202455934 CreatorName Kitagawa, Yasutaka
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.
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.
Publisher	American Chemical Society
Source Title	Journal of Physical Chemistry A
Volume (Issue)	128(39)
Page	8473-8482
Date of Issued	2024-10-03
Language	English
Handle URL	https://hdl.handle.net/11094/98507
PISSN	10895639
eISSN	15205215
Relation.isVersionOf	DOI (Publisher Version) https://doi.org/10.1021/acs.jpca.4c05200
Access Rights	embargoed access
CopyRight	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.
CopyRight	The full-text file will be made open to the public on 3 October 2025 in accordance with the publisher's policy.
oaire:version	Accepted Manuscript
Category	学術雑誌論文 Journal Article

Resource Type	journal article
Local Type	Journal Article
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	English
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	English
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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