Résumé
The origin of the diradical character dependence of the second hyperpolarizability (γ) of neutral singlet diradical systems is clarified based on the perturbation formula of γ using the simplest diradical molecular model with different diradical characters, i.e., H2 under bond dissociation. The enhancement of γ in the intermediate diradical character region turns out to originate from the increasing magnitude of the transition moment between the first and second excited states and the decrease of that between the ground and first excited states, respectively, with the increase in diradical character. This feature confirms that open-shell singlet conjugated molecules with intermediate diradical characters constitute a new class of third-order nonlinear optical systems, whose γ values can be controlled by the diradical character in addition to the conjugation length.
| langue originale | Anglais |
|---|---|
| Numéro d'article | 074113 |
| journal | The journal of chemical physics |
| Volume | 125 |
| Numéro de publication | 7 |
| Les DOIs | |
| état | Publié - 28 août 2006 |
Empreinte digitale
Citer ceci
}
Origin of the enhancement of the second hyperpolarizability of singlet diradical systems with intermediate diradical character. / Nakano, Masayoshi; Kishi, Ryohei; Ohta, Suguru; Takebe, Akihito; Takahashi, Hideaki; Furukawa, Shin Ichi; Kubo, Takashi; Morita, Yasushi; Nakasuji, Kazuhiro; Yamaguchi, Kizashi; Kamada, Kenji; Ohta, Koji; Champagne, Benoît; Botek, Edith.
Dans: The journal of chemical physics, Vol 125, Numéro 7, 074113, 28.08.2006.Résultats de recherche: Contribution à un journal/une revue › Article
TY - JOUR
T1 - Origin of the enhancement of the second hyperpolarizability of singlet diradical systems with intermediate diradical character
AU - Nakano, Masayoshi
AU - Kishi, Ryohei
AU - Ohta, Suguru
AU - Takebe, Akihito
AU - Takahashi, Hideaki
AU - Furukawa, Shin Ichi
AU - Kubo, Takashi
AU - Morita, Yasushi
AU - Nakasuji, Kazuhiro
AU - Yamaguchi, Kizashi
AU - Kamada, Kenji
AU - Ohta, Koji
AU - Champagne, Benoît
AU - Botek, Edith
PY - 2006/8/28
Y1 - 2006/8/28
N2 - The origin of the diradical character dependence of the second hyperpolarizability (γ) of neutral singlet diradical systems is clarified based on the perturbation formula of γ using the simplest diradical molecular model with different diradical characters, i.e., H2 under bond dissociation. The enhancement of γ in the intermediate diradical character region turns out to originate from the increasing magnitude of the transition moment between the first and second excited states and the decrease of that between the ground and first excited states, respectively, with the increase in diradical character. This feature confirms that open-shell singlet conjugated molecules with intermediate diradical characters constitute a new class of third-order nonlinear optical systems, whose γ values can be controlled by the diradical character in addition to the conjugation length.
AB - The origin of the diradical character dependence of the second hyperpolarizability (γ) of neutral singlet diradical systems is clarified based on the perturbation formula of γ using the simplest diradical molecular model with different diradical characters, i.e., H2 under bond dissociation. The enhancement of γ in the intermediate diradical character region turns out to originate from the increasing magnitude of the transition moment between the first and second excited states and the decrease of that between the ground and first excited states, respectively, with the increase in diradical character. This feature confirms that open-shell singlet conjugated molecules with intermediate diradical characters constitute a new class of third-order nonlinear optical systems, whose γ values can be controlled by the diradical character in addition to the conjugation length.
UR - http://www.scopus.com/inward/record.url?scp=33747605074&partnerID=8YFLogxK
U2 - 10.1063/1.2213974
DO - 10.1063/1.2213974
M3 - Article
AN - SCOPUS:33747605074
VL - 125
JO - The journal of chemical physics
JF - The journal of chemical physics
SN - 0021-9606
IS - 7
M1 - 074113
ER -