Open-shell character and second hyperpolarizabilities of one-dimensional chromium(II) chains: Size dependence and bond-length alternation effect

Hitoshi Fukui, Shota Takamuku, Taishi Yamada, Kotaro Fukuda, Taku Takebayashi, Yasuteru Shigeta, Ryohei Kishi, Benoît Champagne, Masayoshi Nakano

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Using the long-range corrected spin-unrestricted density functional theory (LC-UBLYP) method, we have investigated the longitudinal third-order nonlinear optical (NLO) properties, i.e., the second hyperpolarizabilities γ of open-shell singlet one-dimensional (1D) extended metal atom chain (EMAC) systems, chromium(II) chains CrII2n (n = 1-4), with different metal-metal bond lengths from the viewpoint of the open-shell character dependences of each d orbital contribution (dσ, dπ, dδ) to γ and of the chain-length dependence of γ. It turns out that the chain length dependences of the open-shell characters of dπ and dδ orbitals at any metal-metal bond length are negligible, while the dσ open-shell character decreases as a function of chain length. The systems display bell-shaped behaviors of γ as a function of the metal-metal bond length, in which the γ values attain maxima for intermediate dσ open-shell character. The maximum γ value (γmax) exhibits remarkable enhancement as a function of chain length. It is also found that the bond length alternation (BLA) significantly affects the γ values and their chain-length dependences. The present results provide the guiding principles for designing transition-metal complexes with open-shell singlet 1D metallic chains exhibiting large third-order optical nonlinearity.

langue originaleAnglais
Pages (de - à)8700-8707
Nombre de pages8
journalInorganic Chemistry
Volume53
Numéro de publication16
Les DOIs
étatPublié - 18 août 2014

Empreinte digitale

alternations
Bond length
Chromium
chromium
Metals
Chain length
Shells (structures)
metals
Coordination Complexes
orbitals
display devices
Transition metals
Density functional theory
bells
Optical properties
transition metals
nonlinearity
Atoms
density functional theory
optical properties

Citer ceci

Fukui, Hitoshi ; Takamuku, Shota ; Yamada, Taishi ; Fukuda, Kotaro ; Takebayashi, Taku ; Shigeta, Yasuteru ; Kishi, Ryohei ; Champagne, Benoît ; Nakano, Masayoshi. / Open-shell character and second hyperpolarizabilities of one-dimensional chromium(II) chains : Size dependence and bond-length alternation effect. Dans: Inorganic Chemistry. 2014 ; Vol 53, Numéro 16. p. 8700-8707.
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abstract = "Using the long-range corrected spin-unrestricted density functional theory (LC-UBLYP) method, we have investigated the longitudinal third-order nonlinear optical (NLO) properties, i.e., the second hyperpolarizabilities γ of open-shell singlet one-dimensional (1D) extended metal atom chain (EMAC) systems, chromium(II) chains CrII2n (n = 1-4), with different metal-metal bond lengths from the viewpoint of the open-shell character dependences of each d orbital contribution (dσ, dπ, dδ) to γ and of the chain-length dependence of γ. It turns out that the chain length dependences of the open-shell characters of dπ and dδ orbitals at any metal-metal bond length are negligible, while the dσ open-shell character decreases as a function of chain length. The systems display bell-shaped behaviors of γ as a function of the metal-metal bond length, in which the γ values attain maxima for intermediate dσ open-shell character. The maximum γ value (γmax) exhibits remarkable enhancement as a function of chain length. It is also found that the bond length alternation (BLA) significantly affects the γ values and their chain-length dependences. The present results provide the guiding principles for designing transition-metal complexes with open-shell singlet 1D metallic chains exhibiting large third-order optical nonlinearity.",
author = "Hitoshi Fukui and Shota Takamuku and Taishi Yamada and Kotaro Fukuda and Taku Takebayashi and Yasuteru Shigeta and Ryohei Kishi and Beno{\^i}t Champagne and Masayoshi Nakano",
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Open-shell character and second hyperpolarizabilities of one-dimensional chromium(II) chains : Size dependence and bond-length alternation effect. / Fukui, Hitoshi; Takamuku, Shota; Yamada, Taishi; Fukuda, Kotaro; Takebayashi, Taku; Shigeta, Yasuteru; Kishi, Ryohei; Champagne, Benoît; Nakano, Masayoshi.

Dans: Inorganic Chemistry, Vol 53, Numéro 16, 18.08.2014, p. 8700-8707.

Résultats de recherche: Contribution à un journal/une revueArticle

TY - JOUR

T1 - Open-shell character and second hyperpolarizabilities of one-dimensional chromium(II) chains

T2 - Size dependence and bond-length alternation effect

AU - Fukui, Hitoshi

AU - Takamuku, Shota

AU - Yamada, Taishi

AU - Fukuda, Kotaro

AU - Takebayashi, Taku

AU - Shigeta, Yasuteru

AU - Kishi, Ryohei

AU - Champagne, Benoît

AU - Nakano, Masayoshi

PY - 2014/8/18

Y1 - 2014/8/18

N2 - Using the long-range corrected spin-unrestricted density functional theory (LC-UBLYP) method, we have investigated the longitudinal third-order nonlinear optical (NLO) properties, i.e., the second hyperpolarizabilities γ of open-shell singlet one-dimensional (1D) extended metal atom chain (EMAC) systems, chromium(II) chains CrII2n (n = 1-4), with different metal-metal bond lengths from the viewpoint of the open-shell character dependences of each d orbital contribution (dσ, dπ, dδ) to γ and of the chain-length dependence of γ. It turns out that the chain length dependences of the open-shell characters of dπ and dδ orbitals at any metal-metal bond length are negligible, while the dσ open-shell character decreases as a function of chain length. The systems display bell-shaped behaviors of γ as a function of the metal-metal bond length, in which the γ values attain maxima for intermediate dσ open-shell character. The maximum γ value (γmax) exhibits remarkable enhancement as a function of chain length. It is also found that the bond length alternation (BLA) significantly affects the γ values and their chain-length dependences. The present results provide the guiding principles for designing transition-metal complexes with open-shell singlet 1D metallic chains exhibiting large third-order optical nonlinearity.

AB - Using the long-range corrected spin-unrestricted density functional theory (LC-UBLYP) method, we have investigated the longitudinal third-order nonlinear optical (NLO) properties, i.e., the second hyperpolarizabilities γ of open-shell singlet one-dimensional (1D) extended metal atom chain (EMAC) systems, chromium(II) chains CrII2n (n = 1-4), with different metal-metal bond lengths from the viewpoint of the open-shell character dependences of each d orbital contribution (dσ, dπ, dδ) to γ and of the chain-length dependence of γ. It turns out that the chain length dependences of the open-shell characters of dπ and dδ orbitals at any metal-metal bond length are negligible, while the dσ open-shell character decreases as a function of chain length. The systems display bell-shaped behaviors of γ as a function of the metal-metal bond length, in which the γ values attain maxima for intermediate dσ open-shell character. The maximum γ value (γmax) exhibits remarkable enhancement as a function of chain length. It is also found that the bond length alternation (BLA) significantly affects the γ values and their chain-length dependences. The present results provide the guiding principles for designing transition-metal complexes with open-shell singlet 1D metallic chains exhibiting large third-order optical nonlinearity.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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