Iwakura Izumi, Kobayashi Takayoshi, Yabushita Atsushi
University of Electro-Communications, 1-5-1 Chofugaoka, Chofu, Tokyo 182-8585, Japan.
Inorg Chem. 2009 Apr 20;48(8):3523-8. doi: 10.1021/ic801477a.
Ultrafast spectroscopy by a sub-5 fs pulse laser was applied to the simultaneous study of electronic relaxation and vibrational dynamics in Ru(II)(TPP)(CO). The electronic lifetimes of (1)Q(x(1,0))(pi,pi*) and (1)Q(x(0,0))(pi,pi*) were determined to be 230 +/- 70 fs and 1150 +/- 260 fs, respectively. The spectrogram shows the time dependent changes in the vibrational spectrum associated with the spin state change from the Franck-Condon state in the excited singlet state to the triplet state via the curve crossing point between the singlet and triplet potential surfaces. The time constant of the intersystem crossing process was determined to be about 1.0 ps from observed electronic relaxation and vibrational dynamics reflecting the transition from the singlet to triplet electronic excited state.
采用亚5飞秒脉冲激光的超快光谱技术，对Ru(II)(TPP)(CO)中的电子弛豫和振动动力学进行了同步研究。(1)Q(x(1,0))(π,π*)和(1)Q(x(0,0))(π,π*)的电子寿命分别测定为230±70飞秒和1150±260飞秒。光谱图显示了与自旋态变化相关的振动光谱随时间的变化，该变化从激发单重态的弗兰克-康登态通过单重态和三重态势能面之间的曲线交叉点转变为三重态。根据观察到的反映从单重态到三重态电子激发态跃迁的电子弛豫和振动动力学，确定系间窜越过程的时间常数约为1.0皮秒。
