Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: Diradical character and spin multiplicity dependences

Suguru Ohta, Masayoshi Nakano, Takashi Kubo, Kenji Kamada, Koji Ohta, Ryohei Kishi, Nozomi Nakagawa, Benoît Champagne, Edith Botek, Akihito Takebe, Shin Ya Umezaki, Masahito Nate, Hideaki Takahashi, Shin Ichi Furukawa, Yasushi Morita, Kazuhiro Nakasuji, Kizashi Yamaguchi

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

We have investigated the static second hyperpolarizabilities (γ) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene π-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the γ values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of γ, it turns out that the γ values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in y values are not observed between the two π-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on γ. Changing from the singlet to the triplet state, the γ values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of γ is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of γ for phenalenyl radical systems involving π-conjugated linkers by adjusting the diradical character through the change of the linked position of π-conjugated linkers and the spin multiplicity.

langue originaleAnglais
Pages (de - à)3633-3641
Nombre de pages9
journalJournal of physical chemistry A
Volume111
Numéro de publication18
Les DOIs
étatPublié - 10 mai 2007

Empreinte digitale

Acetylene
acetylene
Density functional theory
atomic energy levels
adjusting
density functional theory
predictions

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Ohta, Suguru ; Nakano, Masayoshi ; Kubo, Takashi ; Kamada, Kenji ; Ohta, Koji ; Kishi, Ryohei ; Nakagawa, Nozomi ; Champagne, Benoît ; Botek, Edith ; Takebe, Akihito ; Umezaki, Shin Ya ; Nate, Masahito ; Takahashi, Hideaki ; Furukawa, Shin Ichi ; Morita, Yasushi ; Nakasuji, Kazuhiro ; Yamaguchi, Kizashi. / Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers : Diradical character and spin multiplicity dependences. Dans: Journal of physical chemistry A. 2007 ; Vol 111, Numéro 18. p. 3633-3641.
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title = "Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: Diradical character and spin multiplicity dependences",
abstract = "We have investigated the static second hyperpolarizabilities (γ) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene π-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the γ values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of γ, it turns out that the γ values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in y values are not observed between the two π-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on γ. Changing from the singlet to the triplet state, the γ values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of γ is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of γ for phenalenyl radical systems involving π-conjugated linkers by adjusting the diradical character through the change of the linked position of π-conjugated linkers and the spin multiplicity.",
author = "Suguru Ohta and Masayoshi Nakano and Takashi Kubo and Kenji Kamada and Koji Ohta and Ryohei Kishi and Nozomi Nakagawa and Beno{\^i}t Champagne and Edith Botek and Akihito Takebe and Umezaki, {Shin Ya} and Masahito Nate and Hideaki Takahashi and Furukawa, {Shin Ichi} and Yasushi Morita and Kazuhiro Nakasuji and Kizashi Yamaguchi",
year = "2007",
month = "5",
day = "10",
doi = "10.1021/jp0713662",
language = "English",
volume = "111",
pages = "3633--3641",
journal = "The journal of physical chemistry. A",
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Ohta, S, Nakano, M, Kubo, T, Kamada, K, Ohta, K, Kishi, R, Nakagawa, N, Champagne, B, Botek, E, Takebe, A, Umezaki, SY, Nate, M, Takahashi, H, Furukawa, SI, Morita, Y, Nakasuji, K & Yamaguchi, K 2007, 'Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: Diradical character and spin multiplicity dependences', Journal of physical chemistry A, VOL. 111, Numéro 18, p. 3633-3641. https://doi.org/10.1021/jp0713662

Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers : Diradical character and spin multiplicity dependences. / Ohta, Suguru; Nakano, Masayoshi; Kubo, Takashi; Kamada, Kenji; Ohta, Koji; Kishi, Ryohei; Nakagawa, Nozomi; Champagne, Benoît; Botek, Edith; Takebe, Akihito; Umezaki, Shin Ya; Nate, Masahito; Takahashi, Hideaki; Furukawa, Shin Ichi; Morita, Yasushi; Nakasuji, Kazuhiro; Yamaguchi, Kizashi.

Dans: Journal of physical chemistry A, Vol 111, Numéro 18, 10.05.2007, p. 3633-3641.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers

T2 - Diradical character and spin multiplicity dependences

AU - Ohta, Suguru

AU - Nakano, Masayoshi

AU - Kubo, Takashi

AU - Kamada, Kenji

AU - Ohta, Koji

AU - Kishi, Ryohei

AU - Nakagawa, Nozomi

AU - Champagne, Benoît

AU - Botek, Edith

AU - Takebe, Akihito

AU - Umezaki, Shin Ya

AU - Nate, Masahito

AU - Takahashi, Hideaki

AU - Furukawa, Shin Ichi

AU - Morita, Yasushi

AU - Nakasuji, Kazuhiro

AU - Yamaguchi, Kizashi

PY - 2007/5/10

Y1 - 2007/5/10

N2 - We have investigated the static second hyperpolarizabilities (γ) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene π-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the γ values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of γ, it turns out that the γ values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in y values are not observed between the two π-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on γ. Changing from the singlet to the triplet state, the γ values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of γ is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of γ for phenalenyl radical systems involving π-conjugated linkers by adjusting the diradical character through the change of the linked position of π-conjugated linkers and the spin multiplicity.

AB - We have investigated the static second hyperpolarizabilities (γ) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene π-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the γ values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of γ, it turns out that the γ values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in y values are not observed between the two π-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on γ. Changing from the singlet to the triplet state, the γ values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of γ is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of γ for phenalenyl radical systems involving π-conjugated linkers by adjusting the diradical character through the change of the linked position of π-conjugated linkers and the spin multiplicity.

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U2 - 10.1021/jp0713662

DO - 10.1021/jp0713662

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