期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 123, 期 4, 页码 2056-2065出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.8b10768
关键词
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资金
- People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme (FP7/2007-2013) under REA [609405]
- Danish Council for Independent Research [4002-00272]
- Independent Research Fund Denmark [8021-00347B]
- Lendulet (Momentum) Program of the Hungarian Academy of Sciences [LP2013-59]
The solvent-mediated excited-state dynamics of the COOH-functionalized Fe-carbene photosensitizer [Fe(bmicp)(2)](2+) (bmicp = 2,6-bis(3-methyl-imidazole-1-ylidine)-4-carboxy-pyridine) is studied by time-dependent density functional theory, as well as classical and quantum dynamics simulations. We demonstrate the crucial role of the polar acetonitrile solvent in stabilizing the metal-to-ligand charge transfer (MLCT) states of the investigated molecule using the conductor polarizable continuum model. This leads to dynamics that avoid sub-ps back electron transfer to the metal and an exceptionally long-lived (MLCT)-M-1 state that does not undergo sub-ps (MLCT)-M-1 -> (MLCT)-M-3 intersystem crossing as it is energetically isolated. We identify two components of the excited-state solvent reorganization process: an initial rotation (similar to 300 fs) and diffusional dynamics within the local cage surrounding the rotated solvent molecule (similar to 2 ps). Finally, it is found that the relaxation of the solvent only slightly affects the excited-state population dynamics of [Fe(bmicp)(2)](2+).
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