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 originale | Anglais |
|---|---|
| Pages (de - à) | 8700-8707 |
| Nombre de pages | 8 |
| journal | Inorganic Chemistry |
| Volume | 53 |
| Numéro de publication | 16 |
| Les DOIs | |
| état | Publié - 18 août 2014 |
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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 revue › Article
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.
UR - http://www.scopus.com/inward/record.url?scp=84906248211&partnerID=8YFLogxK
U2 - 10.1021/ic501334p
DO - 10.1021/ic501334p
M3 - Article
AN - SCOPUS:84906248211
VL - 53
SP - 8700
EP - 8707
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 16
ER -