First Excited State Properties and Static Hyperpolarizability of Ruthenium(II) Ammine Complexes
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- 作者：Talgat M. Inerbaev ; Rodion V. Belosludov ; Hiroshi Mizuseki ; Masae Takahashi ; Yoshiyuki Kawazoe
- 刊名：Journal of Chemical Theory and Computation
- 出版年：2006
- 出版时间：September 2006
- 年：2006
- 卷：2
- 期：5
- 页码：1325 - 1334
- 全文大小：296K
- 年卷期：v.2,no.5(September 2006)
- ISSN：1549-9626
文摘
First principles calculations were used to study the electronic excitation energies(E), transition dipole moments (
), and difference of dipole moments between ground and excitedstates (
) for low-lying singlets of the series of ruthenium(II) ammine complexes. Both casesof the gas phase and the acetonitrile solution were investigated in order to explain the discrepancybetween the recent experimental and theoretical results and to develop the optimal way ofestimation for the first static hyperpolarizability in the framework of a two-state model introducedby Oudar and Chemla. The present calculations reveal that the effect of solvent on the electronicproperties of investigated compounds is not only the change of the excitation energy but alsothe increasing of ground-state molecular polarization and intensification of metal-to-ligandintramolecular charge transfer for electronic excitations. These effects lead to increasing of thevalues of and ground-state dipole moment g in solution as compared with the gas-phaseones. The proposed theoretical approach gives good agreement with experiment and allowsone to apply it for designing a new perspective nonlinear optical active organometallics.
), and difference of dipole moments between ground and excitedstates () for low-lying singlets of the series of ruthenium(II) ammine complexes. Both casesof the gas phase and the acetonitrile solution were investigated in order to explain the discrepancybetween the recent experimental and theoretical results and to develop the optimal way ofestimation for the first static hyperpolarizability in the framework of a two-state model introducedby Oudar and Chemla. The present calculations reveal that the effect of solvent on the electronicproperties of investigated compounds is not only the change of the excitation energy but alsothe increasing of ground-state molecular polarization and intensification of metal-to-ligandintramolecular charge transfer for electronic excitations. These effects lead to increasing of thevalues of and ground-state dipole moment g in solution as compared with the gas-phaseones. The proposed theoretical approach gives good agreement with experiment and allowsone to apply it for designing a new perspective nonlinear optical active organometallics.