Theoretical study on the spin state and open-shell character dependences of the second hyperpolarizability in hydrogen chain models

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Résumé

Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

langue originaleAnglais
Numéro d'article042515
journalPhysical Review A - Atomic, Molecular, and Optical Physics
Volume94
Numéro de publication4
Les DOIs
étatPublié - 28 oct. 2016

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hydrogen
configuration interaction
tuning
ground state
approximation
excitation

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    title = "Theoretical study on the spin state and open-shell character dependences of the second hyperpolarizability in hydrogen chain models",
    abstract = "Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.",
    keywords = "quantum chemistry, spin state, open-shell character, second hyperpolarisabillity",
    author = "Hiroshi Matsui and Masayoshi Nakano and Beno{\^i}t Champagne",
    year = "2016",
    month = "10",
    day = "28",
    doi = "10.1103/PhysRevA.94.042515",
    language = "English",
    volume = "94",
    journal = "Physical Review A - Atomic, Molecular, and Optical Physics",
    issn = "1050-2947",
    publisher = "American Physical Society",
    number = "4",

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    TY - JOUR

    T1 - Theoretical study on the spin state and open-shell character dependences of the second hyperpolarizability in hydrogen chain models

    AU - Matsui, Hiroshi

    AU - Nakano, Masayoshi

    AU - Champagne, Benoît

    PY - 2016/10/28

    Y1 - 2016/10/28

    N2 - Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

    AB - Spin state and open-shell character dependences of the static second hyperpolarizability (γ) are theoretically investigated using hydrogen chain models H2n(1≤n≤3) at the full configuration interaction level of approximation. The variation in γ is examined as a function of changing the spin state for a variety of open-shell characters ranging from the closed-shell to pure open-shell states. It is found that (i) in the nearly ground-state closed-shell region, higher-spin states exhibit much larger γ values than the singlet state; (ii) in the intermediate and large open-shell character regions, the singlet state presents the largest γ and γ decreases with the spin multiplicity; and (iii) in the pure open-shell region, all the spin states exhibit negligible γ values. The summation-over-states approach enables rationalizing these findings by considering the primarily contributing excited states. These results reveal that there are two types of molecular design guidelines for enhancing γ values: (a) for nearly closed-shell systems, increasing the spin multiplicity; and (b) for open-shell singlet systems, tuning the open-shell character to the intermediate region.

    KW - quantum chemistry

    KW - spin state

    KW - open-shell character

    KW - second hyperpolarisabillity

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    U2 - 10.1103/PhysRevA.94.042515

    DO - 10.1103/PhysRevA.94.042515

    M3 - Article

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    JO - Physical Review A - Atomic, Molecular, and Optical Physics

    JF - Physical Review A - Atomic, Molecular, and Optical Physics

    SN - 1050-2947

    IS - 4

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