Generalized Mulliken-Hush analysis of electronic coupling interactions in compressed pi-stacked porphyrin-bridge-quinone systems.
Generalized Mulliken-Hush analysis of electronic coupling interactions in compressed pi-stacked porphyrin-bridge-quinone systems.
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压缩 pi 堆叠卟啉-桥-醌系统中电子耦合相互作用的广义 Mulliken-Hush 分析。
DOI：
10.1021/ja050984y
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发表时间：
2005
影响因子：
15
通讯作者：
Beratan,DavidN
中科院分区：
文献类型：
--
作者：
Zheng,Jieru;Kang,YounK;Therien,MichaelJ;Beratan,DavidN
在一系列异常刚性、共面压缩的π-堆叠卟啉-桥-醌体系中研究了给体-受体相互作用。采用两态广义Mulliken-Hush（GMH）方法计算耦合矩阵元。使用GMH方法评估的理论耦合值是通过使用INDO/S方法进行的配置相互作用计算获得的。这种分析的结果是一致的电荷分离和电荷复合反应观察到的相对较软的距离依赖性。对模型结构的理论研究表明，苯基单元主导了供体-受体耦合的中介作用，并且相对较弱的速率随距离的指数衰减是由于这种π电子堆叠的压缩引起的。
Donor−acceptor interactions were investigated in a series of unusually rigid, cofacially compressed π-stacked porphyrin−bridge−quinone systems. The two-state generalized Mulliken−Hush (GMH) approach was used to compute the coupling matrix elements. The theoretical coupling values evaluated with the GMH method were obtained from configuration interaction calculations using the INDO/S method. The results of this analysis are consistent with the comparatively soft distance dependences observed for both the charge separation and charge recombination reactions. Theoretical studies of model structures indicate that the phenyl units dominate the mediation of the donor−acceptor coupling and that the relatively weak exponential decay of rate with distance arises from the compression of this π-electron stack.