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 originale | Anglais |
|---|---|
| journal | Theoretical Chemistry Accounts |
| Volume | 134 |
| Numéro de publication | 3 |
| Les DOIs | |
| état | Publié - 2015 |
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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 revue › Article
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
UR - http://www.scopus.com/inward/record.url?scp=84922375845&partnerID=8YFLogxK
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 -