Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K)

Zong Jun Li, Fang Fang Wang, Zhi Ru Li, Hong Liang Xu, Xu Ri Huang, Di Wu, Wei Chen, Guang Tao Yu, Feng Long Gu, Yuriko Aoki

    Research output: Contribution to journalArticle

    90 Citations (Scopus)

    Abstract

    The interesting radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K) are a particular class of charge transfer complexes with excess electron. The ground states of these complexes are triplet. The C2v symmetry geometrical structures of the M2•+TCNQ•- (M = Li, Na, K) with all-real frequencies are obtained at the density functional theory (DFT) B3LYP/6-31+G(d) level. All calculations of electric properties in this paper have been carried out at the restricted open-shell second order Møller-Plesset perturbation theory (ROMP2) level. Owing to existing excess electron (from the polarized alkali metal atoms) these charge transfer complexes exhibit large nonlinear optical (NLO) responses dominated by excess electron transitions. For these radical ion pair salts M2 •+TCNQ•-, the static first hyperpolarizabilities (β0) are large. The order of β0 values is 19 203 (M = Li) < 24 140 (M = Na) < 29 065 a.u. (M = K). Specially, the second hyperpolarizability (γ0) of the complexes with excess electron is obtained for the first time. These static second hyperpolarizabilities are also large. The order of γ0 values is 2 213 006 (M = Li) < 3 136 754 (M = Na) < 7 905 623 a.u. (M = K). Among the three structures, K2•+TCNQ•- has the largest γ0 value to be 7.9 × 106 a.u. (3982 × 10-36 esu), which is about 9 times larger than that of the intramolecular charge transfer complex σ-arylvinylidene trans-[Ru(4-C=CHC6H4C=CC6H4NO 2)Cl(dppm)2]PF6 [Hurst et al., Organometallics, 2001, 20, 4664]. The present investigation provides a new kind of candidates for the high-performance NLO materials.

    Original languageEnglish
    Pages (from-to)402-408
    Number of pages7
    JournalPhysical Chemistry Chemical Physics
    Volume11
    Issue number2
    DOIs
    Publication statusPublished - Jan 6 2009

    Fingerprint

    electron transitions
    Electron transitions
    Salts
    charge transfer
    Ions
    salts
    Charge transfer
    Electrons
    ions
    electrons
    optical materials
    Alkali Metals
    alkali metals
    Optical materials
    Organometallics
    perturbation theory
    Ground state
    density functional theory
    Density functional theory
    Electric properties

    All Science Journal Classification (ASJC) codes

    • Physics and Astronomy(all)
    • Physical and Theoretical Chemistry

    Cite this

    Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K). / Li, Zong Jun; Wang, Fang Fang; Li, Zhi Ru; Xu, Hong Liang; Huang, Xu Ri; Wu, Di; Chen, Wei; Yu, Guang Tao; Gu, Feng Long; Aoki, Yuriko.

    In: Physical Chemistry Chemical Physics, Vol. 11, No. 2, 06.01.2009, p. 402-408.

    Research output: Contribution to journalArticle

    Li, Zong Jun ; Wang, Fang Fang ; Li, Zhi Ru ; Xu, Hong Liang ; Huang, Xu Ri ; Wu, Di ; Chen, Wei ; Yu, Guang Tao ; Gu, Feng Long ; Aoki, Yuriko. / Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K). In: Physical Chemistry Chemical Physics. 2009 ; Vol. 11, No. 2. pp. 402-408.
    @article{4d55fd52efc44ee1a753c23ad98416d4,
    title = "Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K)",
    abstract = "The interesting radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K) are a particular class of charge transfer complexes with excess electron. The ground states of these complexes are triplet. The C2v symmetry geometrical structures of the M2•+TCNQ•- (M = Li, Na, K) with all-real frequencies are obtained at the density functional theory (DFT) B3LYP/6-31+G(d) level. All calculations of electric properties in this paper have been carried out at the restricted open-shell second order M{\o}ller-Plesset perturbation theory (ROMP2) level. Owing to existing excess electron (from the polarized alkali metal atoms) these charge transfer complexes exhibit large nonlinear optical (NLO) responses dominated by excess electron transitions. For these radical ion pair salts M2 •+TCNQ•-, the static first hyperpolarizabilities (β0) are large. The order of β0 values is 19 203 (M = Li) < 24 140 (M = Na) < 29 065 a.u. (M = K). Specially, the second hyperpolarizability (γ0) of the complexes with excess electron is obtained for the first time. These static second hyperpolarizabilities are also large. The order of γ0 values is 2 213 006 (M = Li) < 3 136 754 (M = Na) < 7 905 623 a.u. (M = K). Among the three structures, K2•+TCNQ•- has the largest γ0 value to be 7.9 × 106 a.u. (3982 × 10-36 esu), which is about 9 times larger than that of the intramolecular charge transfer complex σ-arylvinylidene trans-[Ru(4-C=CHC6H4C=CC6H4NO 2)Cl(dppm)2]PF6 [Hurst et al., Organometallics, 2001, 20, 4664]. The present investigation provides a new kind of candidates for the high-performance NLO materials.",
    author = "Li, {Zong Jun} and Wang, {Fang Fang} and Li, {Zhi Ru} and Xu, {Hong Liang} and Huang, {Xu Ri} and Di Wu and Wei Chen and Yu, {Guang Tao} and Gu, {Feng Long} and Yuriko Aoki",
    year = "2009",
    month = "1",
    day = "6",
    doi = "10.1039/b809161g",
    language = "English",
    volume = "11",
    pages = "402--408",
    journal = "Physical Chemistry Chemical Physics",
    issn = "1463-9076",
    publisher = "Royal Society of Chemistry",
    number = "2",

    }

    TY - JOUR

    T1 - Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K)

    AU - Li, Zong Jun

    AU - Wang, Fang Fang

    AU - Li, Zhi Ru

    AU - Xu, Hong Liang

    AU - Huang, Xu Ri

    AU - Wu, Di

    AU - Chen, Wei

    AU - Yu, Guang Tao

    AU - Gu, Feng Long

    AU - Aoki, Yuriko

    PY - 2009/1/6

    Y1 - 2009/1/6

    N2 - The interesting radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K) are a particular class of charge transfer complexes with excess electron. The ground states of these complexes are triplet. The C2v symmetry geometrical structures of the M2•+TCNQ•- (M = Li, Na, K) with all-real frequencies are obtained at the density functional theory (DFT) B3LYP/6-31+G(d) level. All calculations of electric properties in this paper have been carried out at the restricted open-shell second order Møller-Plesset perturbation theory (ROMP2) level. Owing to existing excess electron (from the polarized alkali metal atoms) these charge transfer complexes exhibit large nonlinear optical (NLO) responses dominated by excess electron transitions. For these radical ion pair salts M2 •+TCNQ•-, the static first hyperpolarizabilities (β0) are large. The order of β0 values is 19 203 (M = Li) < 24 140 (M = Na) < 29 065 a.u. (M = K). Specially, the second hyperpolarizability (γ0) of the complexes with excess electron is obtained for the first time. These static second hyperpolarizabilities are also large. The order of γ0 values is 2 213 006 (M = Li) < 3 136 754 (M = Na) < 7 905 623 a.u. (M = K). Among the three structures, K2•+TCNQ•- has the largest γ0 value to be 7.9 × 106 a.u. (3982 × 10-36 esu), which is about 9 times larger than that of the intramolecular charge transfer complex σ-arylvinylidene trans-[Ru(4-C=CHC6H4C=CC6H4NO 2)Cl(dppm)2]PF6 [Hurst et al., Organometallics, 2001, 20, 4664]. The present investigation provides a new kind of candidates for the high-performance NLO materials.

    AB - The interesting radical ion pair salts M2 •+TCNQ•- (M = Li, Na, K) are a particular class of charge transfer complexes with excess electron. The ground states of these complexes are triplet. The C2v symmetry geometrical structures of the M2•+TCNQ•- (M = Li, Na, K) with all-real frequencies are obtained at the density functional theory (DFT) B3LYP/6-31+G(d) level. All calculations of electric properties in this paper have been carried out at the restricted open-shell second order Møller-Plesset perturbation theory (ROMP2) level. Owing to existing excess electron (from the polarized alkali metal atoms) these charge transfer complexes exhibit large nonlinear optical (NLO) responses dominated by excess electron transitions. For these radical ion pair salts M2 •+TCNQ•-, the static first hyperpolarizabilities (β0) are large. The order of β0 values is 19 203 (M = Li) < 24 140 (M = Na) < 29 065 a.u. (M = K). Specially, the second hyperpolarizability (γ0) of the complexes with excess electron is obtained for the first time. These static second hyperpolarizabilities are also large. The order of γ0 values is 2 213 006 (M = Li) < 3 136 754 (M = Na) < 7 905 623 a.u. (M = K). Among the three structures, K2•+TCNQ•- has the largest γ0 value to be 7.9 × 106 a.u. (3982 × 10-36 esu), which is about 9 times larger than that of the intramolecular charge transfer complex σ-arylvinylidene trans-[Ru(4-C=CHC6H4C=CC6H4NO 2)Cl(dppm)2]PF6 [Hurst et al., Organometallics, 2001, 20, 4664]. The present investigation provides a new kind of candidates for the high-performance NLO materials.

    UR - http://www.scopus.com/inward/record.url?scp=58149087014&partnerID=8YFLogxK

    UR - http://www.scopus.com/inward/citedby.url?scp=58149087014&partnerID=8YFLogxK

    U2 - 10.1039/b809161g

    DO - 10.1039/b809161g

    M3 - Article

    C2 - 19088997

    AN - SCOPUS:58149087014

    VL - 11

    SP - 402

    EP - 408

    JO - Physical Chemistry Chemical Physics

    JF - Physical Chemistry Chemical Physics

    SN - 1463-9076

    IS - 2

    ER -