Diradicalology in Third-Order Nonlinear Optical Systems: Second Hyperpolarizabilities of Acetylene-Linked Phenalenyl-Based Superpolyenes

Masayoshi Nakano, Ryohei Kishi, Hitoshi Fukui, Takuya Minami, Kyohei Yoneda, Shu Minamide, Yudai Inoue, Taishi Yamada, Soichi Ito, Shabbir Muhammad, Yasuteru Shigeta, Takashi Kubo, Benoît Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

From the viewpoint of "diradical character," referred to as "diradicalology," we investigate the second hyperpolarizability γ - the molecular third-order nonlinear optical (NLO) property - of one-dimensional supermolecular systems composed of acetylene-linked phenalenyl/pyrene rings using long-range corrected spin-unrestricted density functional theory. It turns out that the pyrene-based superpolyenes (Py-n) behave like closed-shell systems, whereas phenalenyl-based superpolyenes (Ph1-n and Ph2-n) have different diradical characters depending on the linked form, that is, Ph1-n and Ph2-n have intermediate and pure diradical characters, respectively. In comparison with Py-n and Ph2-n, the longitudinal γ of Ph1-n is significantly larger, and it displays larger enhancement as a function of system size. Substitutions to the terminal rings by donor (NH2) and acceptor (NO2) groups further enhance γ in Ph1-n, more than in Ph2-n and Py-n. These results are in agreement with the structure-property relationships derived for open-shell NLO systems with symmetric and asymmetric charge distributions (Nakano et al., J. Chem. Phys. 2010, 133, 154302).

langue originaleAnglais
Pages (de - à)585-591
Nombre de pages7
journalInternational Journal of Quantum Chemistry
Volume113
Numéro de publication4
Les DOIs
étatPublié - 15 févr. 2013

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Acetylene
pyrenes
Optical systems
acetylene
rings
Charge distribution
charge distribution
Density functional theory
Substitution reactions
Optical properties
substitutes
density functional theory
optical properties
augmentation
pyrene

Citer ceci

Nakano, Masayoshi ; Kishi, Ryohei ; Fukui, Hitoshi ; Minami, Takuya ; Yoneda, Kyohei ; Minamide, Shu ; Inoue, Yudai ; Yamada, Taishi ; Ito, Soichi ; Muhammad, Shabbir ; Shigeta, Yasuteru ; Kubo, Takashi ; Champagne, Benoît. / Diradicalology in Third-Order Nonlinear Optical Systems: Second Hyperpolarizabilities of Acetylene-Linked Phenalenyl-Based Superpolyenes. Dans: International Journal of Quantum Chemistry. 2013 ; Vol 113, Numéro 4. p. 585-591.
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abstract = "From the viewpoint of {"}diradical character,{"} referred to as {"}diradicalology,{"} we investigate the second hyperpolarizability γ - the molecular third-order nonlinear optical (NLO) property - of one-dimensional supermolecular systems composed of acetylene-linked phenalenyl/pyrene rings using long-range corrected spin-unrestricted density functional theory. It turns out that the pyrene-based superpolyenes (Py-n) behave like closed-shell systems, whereas phenalenyl-based superpolyenes (Ph1-n and Ph2-n) have different diradical characters depending on the linked form, that is, Ph1-n and Ph2-n have intermediate and pure diradical characters, respectively. In comparison with Py-n and Ph2-n, the longitudinal γ of Ph1-n is significantly larger, and it displays larger enhancement as a function of system size. Substitutions to the terminal rings by donor (NH2) and acceptor (NO2) groups further enhance γ in Ph1-n, more than in Ph2-n and Py-n. These results are in agreement with the structure-property relationships derived for open-shell NLO systems with symmetric and asymmetric charge distributions (Nakano et al., J. Chem. Phys. 2010, 133, 154302).",
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author = "Masayoshi Nakano and Ryohei Kishi and Hitoshi Fukui and Takuya Minami and Kyohei Yoneda and Shu Minamide and Yudai Inoue and Taishi Yamada and Soichi Ito and Shabbir Muhammad and Yasuteru Shigeta and Takashi Kubo and Beno{\^i}t Champagne",
note = "Meeting QSCP XVII",
year = "2013",
month = "2",
day = "15",
doi = "10.1002/qua.24035",
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Nakano, M, Kishi, R, Fukui, H, Minami, T, Yoneda, K, Minamide, S, Inoue, Y, Yamada, T, Ito, S, Muhammad, S, Shigeta, Y, Kubo, T & Champagne, B 2013, 'Diradicalology in Third-Order Nonlinear Optical Systems: Second Hyperpolarizabilities of Acetylene-Linked Phenalenyl-Based Superpolyenes', International Journal of Quantum Chemistry, VOL. 113, Numéro 4, p. 585-591. https://doi.org/10.1002/qua.24035

Diradicalology in Third-Order Nonlinear Optical Systems: Second Hyperpolarizabilities of Acetylene-Linked Phenalenyl-Based Superpolyenes. / Nakano, Masayoshi; Kishi, Ryohei; Fukui, Hitoshi; Minami, Takuya; Yoneda, Kyohei; Minamide, Shu; Inoue, Yudai; Yamada, Taishi; Ito, Soichi; Muhammad, Shabbir; Shigeta, Yasuteru; Kubo, Takashi; Champagne, Benoît.

Dans: International Journal of Quantum Chemistry, Vol 113, Numéro 4, 15.02.2013, p. 585-591.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Diradicalology in Third-Order Nonlinear Optical Systems: Second Hyperpolarizabilities of Acetylene-Linked Phenalenyl-Based Superpolyenes

AU - Nakano, Masayoshi

AU - Kishi, Ryohei

AU - Fukui, Hitoshi

AU - Minami, Takuya

AU - Yoneda, Kyohei

AU - Minamide, Shu

AU - Inoue, Yudai

AU - Yamada, Taishi

AU - Ito, Soichi

AU - Muhammad, Shabbir

AU - Shigeta, Yasuteru

AU - Kubo, Takashi

AU - Champagne, Benoît

N1 - Meeting QSCP XVII

PY - 2013/2/15

Y1 - 2013/2/15

N2 - From the viewpoint of "diradical character," referred to as "diradicalology," we investigate the second hyperpolarizability γ - the molecular third-order nonlinear optical (NLO) property - of one-dimensional supermolecular systems composed of acetylene-linked phenalenyl/pyrene rings using long-range corrected spin-unrestricted density functional theory. It turns out that the pyrene-based superpolyenes (Py-n) behave like closed-shell systems, whereas phenalenyl-based superpolyenes (Ph1-n and Ph2-n) have different diradical characters depending on the linked form, that is, Ph1-n and Ph2-n have intermediate and pure diradical characters, respectively. In comparison with Py-n and Ph2-n, the longitudinal γ of Ph1-n is significantly larger, and it displays larger enhancement as a function of system size. Substitutions to the terminal rings by donor (NH2) and acceptor (NO2) groups further enhance γ in Ph1-n, more than in Ph2-n and Py-n. These results are in agreement with the structure-property relationships derived for open-shell NLO systems with symmetric and asymmetric charge distributions (Nakano et al., J. Chem. Phys. 2010, 133, 154302).

AB - From the viewpoint of "diradical character," referred to as "diradicalology," we investigate the second hyperpolarizability γ - the molecular third-order nonlinear optical (NLO) property - of one-dimensional supermolecular systems composed of acetylene-linked phenalenyl/pyrene rings using long-range corrected spin-unrestricted density functional theory. It turns out that the pyrene-based superpolyenes (Py-n) behave like closed-shell systems, whereas phenalenyl-based superpolyenes (Ph1-n and Ph2-n) have different diradical characters depending on the linked form, that is, Ph1-n and Ph2-n have intermediate and pure diradical characters, respectively. In comparison with Py-n and Ph2-n, the longitudinal γ of Ph1-n is significantly larger, and it displays larger enhancement as a function of system size. Substitutions to the terminal rings by donor (NH2) and acceptor (NO2) groups further enhance γ in Ph1-n, more than in Ph2-n and Py-n. These results are in agreement with the structure-property relationships derived for open-shell NLO systems with symmetric and asymmetric charge distributions (Nakano et al., J. Chem. Phys. 2010, 133, 154302).

KW - density functional theory

KW - diradical character

KW - open shell

KW - phenalenyl

KW - second hyperpolarizability

UR - http://www.scopus.com/inward/record.url?scp=84872982214&partnerID=8YFLogxK

U2 - 10.1002/qua.24035

DO - 10.1002/qua.24035

M3 - Article

AN - SCOPUS:84872982214

VL - 113

SP - 585

EP - 591

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 4

ER -