Excited state relaxation dynamics of the zinc(II) tetraphenylporphine cation radical.
Excited state relaxation dynamics of the zinc(II) tetraphenylporphine cation radical.
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四苯基卟啉锌 (II) 阳离子自由基的激发态弛豫动力学。
DOI：
10.1021/jp053136y
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
Rodgers,MichaelAJ
中科院分区：
文献类型：
--
作者：
Okhrimenko,AlbertN;Gusev,AlexeyV;Rodgers,MichaelAJ
报道了一种研究四苯基卟啉锌（II）阳离子自由基的电子物理性质的新方法。它采用控制电位库仑法和飞秒吸收光谱法的组合。π-阳离子物种的17 ps的快速瞬态寿命起源于a2 uHOMO阳离子轨道的非常有效的混合，该轨道将电子密度主要置于吡咯氮和金属d-轨道上。这就解释了为什么没有阳离子物质的排放。这种非辐射衰变过程可能阐明光合作用系统中发生的过程，当一个电子从卟啉部分被删除，并产生空穴。
A new technique employed to study the photophysical properties of the zinc(II) tetraphenylporphine cation radical is reported. It employs a combination of controlled potential coulometry and femtosecond absorption spectrometry. The fast transient lifetime of 17 ps of the π-cation species originates in very efficient mixing of the a2uHOMO cation orbital that places electronic density mainly on pyrrolic nitrogens and metal d-orbitals. That explains the lack of any emission of the cationic species. This nonradiative decay process might elucidate the processes taking place in photosynthetic systems when an electron is removed from the porphyrinic moiety and the hole is produced.