Effect of the complexant shape on the large first hyperpolarizability of alkalides Li+(NH3)4M-

Ying Qi Jing, Zhi Ru Li, Di Wu, Ying Li, Bing Qiang Wang, Feng Long Gu, Yuriko Aoki

    Research output: Contribution to journalArticle

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    Abstract

    The effect of complexant shape effect on the first hyperpolarizability β0, of alkalides Li+(NH3) 4M- (M=Li, Na, K) was explored. At the MP2/6-311 ++ G level, Li+(NH3)4M- (M=Li, Na, K) have considerable β0 values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li + (calix[4]pyrrole)M-, a complexant shape effect in Li+(NH3)4M- is detected. The β0 values of Li+(NH3)4M - with the "smaller", inorganic, Td-symmetric (NH3)4 complexant are more than four times larger than those of Li+(calix[4]pyrrole)M- with the "larger", organic C4v-symmetric calix[4]pyrrole complexant. The ratios of the β0 values of Li+(NH 3)4M- and Li+(calix[4]pyrrole)M - are 6.57 (M = Li), 6.55 (M = Na), and 5.77 (M = K). In the Li +(NH3)4M- systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M- is -0.667 (M = Li) > -0.644 (M = Na) > -0.514 (M = K), while the order of the oscillator strengths in the crucial transition is 0.351 (M = Li) < 0.360 (M = Na) < 0.467 (M = K). This indicates that complexant shape effects are strong, and consequently the β0 values of Li +(NH3)4M- are found to be β0 = 70 295 (M = Li) < 96 780 (M = Na) < 185 805 a.u. (M = K). This work reveals that the use of a high-symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.

    Original languageEnglish
    Pages (from-to)1759-1763
    Number of pages5
    JournalChemPhysChem
    Volume7
    Issue number8
    DOIs
    Publication statusPublished - Aug 11 2006

    Fingerprint

    pyrroles
    oscillator strengths
    Anions
    Doping (additives)
    anions
    Alkali Metals
    Alkalies
    alkali metals
    Charge transfer
    alkalies
    charge transfer
    calix(4)pyrrole
    Electrons
    symmetry
    electrons

    All Science Journal Classification (ASJC) codes

    • Atomic and Molecular Physics, and Optics
    • Physical and Theoretical Chemistry

    Cite this

    Effect of the complexant shape on the large first hyperpolarizability of alkalides Li+(NH3)4M-. / Jing, Ying Qi; Li, Zhi Ru; Wu, Di; Li, Ying; Wang, Bing Qiang; Gu, Feng Long; Aoki, Yuriko.

    In: ChemPhysChem, Vol. 7, No. 8, 11.08.2006, p. 1759-1763.

    Research output: Contribution to journalArticle

    Jing, Ying Qi ; Li, Zhi Ru ; Wu, Di ; Li, Ying ; Wang, Bing Qiang ; Gu, Feng Long ; Aoki, Yuriko. / Effect of the complexant shape on the large first hyperpolarizability of alkalides Li+(NH3)4M-. In: ChemPhysChem. 2006 ; Vol. 7, No. 8. pp. 1759-1763.
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    abstract = "The effect of complexant shape effect on the first hyperpolarizability β0, of alkalides Li+(NH3) 4M- (M=Li, Na, K) was explored. At the MP2/6-311 ++ G level, Li+(NH3)4M- (M=Li, Na, K) have considerable β0 values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li + (calix[4]pyrrole)M-, a complexant shape effect in Li+(NH3)4M- is detected. The β0 values of Li+(NH3)4M - with the {"}smaller{"}, inorganic, Td-symmetric (NH3)4 complexant are more than four times larger than those of Li+(calix[4]pyrrole)M- with the {"}larger{"}, organic C4v-symmetric calix[4]pyrrole complexant. The ratios of the β0 values of Li+(NH 3)4M- and Li+(calix[4]pyrrole)M - are 6.57 (M = Li), 6.55 (M = Na), and 5.77 (M = K). In the Li +(NH3)4M- systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M- is -0.667 (M = Li) > -0.644 (M = Na) > -0.514 (M = K), while the order of the oscillator strengths in the crucial transition is 0.351 (M = Li) < 0.360 (M = Na) < 0.467 (M = K). This indicates that complexant shape effects are strong, and consequently the β0 values of Li +(NH3)4M- are found to be β0 = 70 295 (M = Li) < 96 780 (M = Na) < 185 805 a.u. (M = K). This work reveals that the use of a high-symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.",
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    AU - Jing, Ying Qi

    AU - Li, Zhi Ru

    AU - Wu, Di

    AU - Li, Ying

    AU - Wang, Bing Qiang

    AU - Gu, Feng Long

    AU - Aoki, Yuriko

    PY - 2006/8/11

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    N2 - The effect of complexant shape effect on the first hyperpolarizability β0, of alkalides Li+(NH3) 4M- (M=Li, Na, K) was explored. At the MP2/6-311 ++ G level, Li+(NH3)4M- (M=Li, Na, K) have considerable β0 values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li + (calix[4]pyrrole)M-, a complexant shape effect in Li+(NH3)4M- is detected. The β0 values of Li+(NH3)4M - with the "smaller", inorganic, Td-symmetric (NH3)4 complexant are more than four times larger than those of Li+(calix[4]pyrrole)M- with the "larger", organic C4v-symmetric calix[4]pyrrole complexant. The ratios of the β0 values of Li+(NH 3)4M- and Li+(calix[4]pyrrole)M - are 6.57 (M = Li), 6.55 (M = Na), and 5.77 (M = K). In the Li +(NH3)4M- systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M- is -0.667 (M = Li) > -0.644 (M = Na) > -0.514 (M = K), while the order of the oscillator strengths in the crucial transition is 0.351 (M = Li) < 0.360 (M = Na) < 0.467 (M = K). This indicates that complexant shape effects are strong, and consequently the β0 values of Li +(NH3)4M- are found to be β0 = 70 295 (M = Li) < 96 780 (M = Na) < 185 805 a.u. (M = K). This work reveals that the use of a high-symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.

    AB - The effect of complexant shape effect on the first hyperpolarizability β0, of alkalides Li+(NH3) 4M- (M=Li, Na, K) was explored. At the MP2/6-311 ++ G level, Li+(NH3)4M- (M=Li, Na, K) have considerable β0 values due to excess electrons from chemical doping and charge transfer. By comparison with the alkalides Li + (calix[4]pyrrole)M-, a complexant shape effect in Li+(NH3)4M- is detected. The β0 values of Li+(NH3)4M - with the "smaller", inorganic, Td-symmetric (NH3)4 complexant are more than four times larger than those of Li+(calix[4]pyrrole)M- with the "larger", organic C4v-symmetric calix[4]pyrrole complexant. The ratios of the β0 values of Li+(NH 3)4M- and Li+(calix[4]pyrrole)M - are 6.57 (M = Li), 6.55 (M = Na), and 5.77 (M = K). In the Li +(NH3)4M- systems, the NBO charge and oscillator strength are found to monotonically depend on the atomic number of the alkali metal anion. The order of the NBO charges of the alkali anions M- is -0.667 (M = Li) > -0.644 (M = Na) > -0.514 (M = K), while the order of the oscillator strengths in the crucial transition is 0.351 (M = Li) < 0.360 (M = Na) < 0.467 (M = K). This indicates that complexant shape effects are strong, and consequently the β0 values of Li +(NH3)4M- are found to be β0 = 70 295 (M = Li) < 96 780 (M = Na) < 185 805 a.u. (M = K). This work reveals that the use of a high-symmetry complexant is an important factor that should be taken into account when enhancing the first hyperpolarizability of alkalides by chemical doping.

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