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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Ultrafast Excited-State Dynamics of Re(CO)_3Cl(dcbpy) in Solution and on Nanocrystalline TiO_2 and ZrO_2 Thin Films
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Ultrafast Excited-State Dynamics of Re(CO)_3Cl(dcbpy) in Solution and on Nanocrystalline TiO_2 and ZrO_2 Thin Films

机译：溶液中以及纳米TiO_2和ZrO_2薄膜上Re（CO）_3Cl（dcbpy）的超快激发态动力学

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摘要

Femtosecond infrared spectroscopy was used to study the excited-state dynamics of Re(CO)_3Cl(dcbpy) in DMF solution and on the surface of ZrO_2 and TiO_2 nanocrystalline thin films. For Re(CO)_3Cl(dcbpy) in DMF solution, we observed a long-lived ~3MLCT state with a lifetime of >1 ns. The frequencies for the CO stretching bands were blue-shifted compared to those in the ground state, consistent with the metal-to-ligand charge-transfer nature of the excited state. Rapid spectral evolution of the excited-state CO stretching bands was observed within the first 12 ps. For Re(CO)_3Cl(dcbpy) on ZrO-2 thin films, a similar ~3MLCT state was observed. However, the spectral blue shift was much less pronounced and occurred on a faster time scale. We suggest that vibrational relaxation is the primary contribution to the spectral evolution of Re(CO)-3Cl(dcbpy) on the ZrO_2 film, whereas both vibrational relaxation and solvation of the MLCT state contribute to the spectral evolution in DMF solution. The excited-state decay rate of Re(CO)_3Cl(dcbpy) on ZrO_2 films was faster than the rate in DMF and increased with higher excitation power. The faster excited-state decay is attributed to the occurrence of an excited-state quenching process between neighboring excited molecules on the film. For Re(CO)_3Cl(dcbpy)-sensitized TiO_2 thin films, broad mid-IR absorption of injected electrons was observed. The rise time of the electron absorption signal in TiO_2 was found to be less than 100 fs. In addition, the adsorbate CO stretching bands were also observed. We discuss the detailed information about the electron-injection process that can be obtained from the adsorbate vibrational spectra.
机译：飞秒红外光谱用于研究DMF溶液中ZrO_2和TiO_2纳米晶薄膜表面Re（CO）_3Cl（dcbpy）的激发态动力学。对于DMF溶液中的Re（CO）_3Cl（dcbpy），我们观察到了寿命较长的〜3MLCT状态，其寿命> 1 ns。与基态相比，CO拉伸带的频率蓝移，这与激发态的金属到配体的电荷转移性质一致。在最初的12 ps内观察到了激发态CO拉伸带的快速光谱演化。对于ZrO-2薄膜上的Re（CO）_3Cl（dcbpy），观察到相似的〜3MLCT状态。然而，光谱的蓝移不那么明显，并且发生在更快的时间尺度上。我们认为，振动弛豫是ZrO_2薄膜上Re（CO）-3Cl（dcbpy）光谱演化的主要贡献，而MLCT状态的振动弛豫和溶剂化都对DMF溶液中的光谱演化有贡献。 Re（CO）_3Cl（dcbpy）在ZrO_2薄膜上的激发态衰减速率比DMF中的速率更快，并且随着更高的激发功率而增加。更快的激发态衰减归因于膜上相邻激发分子之间的激发态猝灭过程。对于Re（CO）_3Cl（dcbpy）敏化的TiO_2薄膜，观察到注入电子的宽中红外吸收。发现TiO_2中电子吸收信号的上升时间小于100fs。另外，还观察到吸附物CO拉伸带。我们讨论了有关可从吸附物振动光谱获得的电子注入过程的详细信息。

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