Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems

Masayoshi Nakano, Benoît Champagne

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

Using a two-site valence configuration interaction model, we reveal the diradical character (y) dependences of the third-harmonic generation (THG) spectra of singlet diradicaloids, which are described by the photon energy-dependent THG second hyperpolarizabilities γ. We particularly examine three- and two-photon resonance peaks associated with the dipole-allowed transition to the first excited state and with the dipole-forbidden transition to the second excited state, respectively. When increasing y, both peaks move to lower-energy region and become close to each other. Although the THG γ spectral intensities show resonance enhancements for any y value, we observe for THG γ the same bell-shape behavior as a function of y, as for the static γ, irrespective of the photon energy.

langue originaleAnglais
journalTheoretical Chemistry Accounts
Volume134
Numéro de publication3
Les DOIs
étatPublié - 2015

Empreinte digitale

Harmonic generation
harmonic generations
Photons
photons
Electron transitions
Excited states
dipoles
forbidden transitions
bells
configuration interaction
excitation
energy
valence
augmentation

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    title = "Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems",
    abstract = "Using a two-site valence configuration interaction model, we reveal the diradical character (y) dependences of the third-harmonic generation (THG) spectra of singlet diradicaloids, which are described by the photon energy-dependent THG second hyperpolarizabilities γ. We particularly examine three- and two-photon resonance peaks associated with the dipole-allowed transition to the first excited state and with the dipole-forbidden transition to the second excited state, respectively. When increasing y, both peaks move to lower-energy region and become close to each other. Although the THG γ spectral intensities show resonance enhancements for any y value, we observe for THG γ the same bell-shape behavior as a function of y, as for the static γ, irrespective of the photon energy.",
    keywords = "Diradical, Open-shell molecule, Second hyperpolarizability, Third-harmonic generation spectra",
    author = "Masayoshi Nakano and Beno{\^i}t Champagne",
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    volume = "134",
    journal = "Theoretical Chemistry Accounts: Theory, Computation, and Modeling",
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    Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems. / Nakano, Masayoshi; Champagne, Benoît.

    Dans: Theoretical Chemistry Accounts, Vol 134, Numéro 3, 2015.

    Résultats de recherche: Contribution à un journal/une revueArticle

    TY - JOUR

    T1 - Diradical character dependence of third-harmonic generation spectra in open-shell singlet systems

    AU - Nakano, Masayoshi

    AU - Champagne, Benoît

    PY - 2015

    Y1 - 2015

    N2 - Using a two-site valence configuration interaction model, we reveal the diradical character (y) dependences of the third-harmonic generation (THG) spectra of singlet diradicaloids, which are described by the photon energy-dependent THG second hyperpolarizabilities γ. We particularly examine three- and two-photon resonance peaks associated with the dipole-allowed transition to the first excited state and with the dipole-forbidden transition to the second excited state, respectively. When increasing y, both peaks move to lower-energy region and become close to each other. Although the THG γ spectral intensities show resonance enhancements for any y value, we observe for THG γ the same bell-shape behavior as a function of y, as for the static γ, irrespective of the photon energy.

    AB - Using a two-site valence configuration interaction model, we reveal the diradical character (y) dependences of the third-harmonic generation (THG) spectra of singlet diradicaloids, which are described by the photon energy-dependent THG second hyperpolarizabilities γ. We particularly examine three- and two-photon resonance peaks associated with the dipole-allowed transition to the first excited state and with the dipole-forbidden transition to the second excited state, respectively. When increasing y, both peaks move to lower-energy region and become close to each other. Although the THG γ spectral intensities show resonance enhancements for any y value, we observe for THG γ the same bell-shape behavior as a function of y, as for the static γ, irrespective of the photon energy.

    KW - Diradical

    KW - Open-shell molecule

    KW - Second hyperpolarizability

    KW - Third-harmonic generation spectra

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    U2 - 10.1007/s00214-015-1618-6

    DO - 10.1007/s00214-015-1618-6

    M3 - Article

    VL - 134

    JO - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

    JF - Theoretical Chemistry Accounts: Theory, Computation, and Modeling

    SN - 1432-881X

    IS - 3

    ER -