模型DNA碱基对激发态双质子转移的一致和逐步争论的前言和后记

H. Sekiya, Kenji Sakota
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引用次数: 0

摘要

以共面7-氮杂二聚体(7ai2)为模型碱基对,研究了其激发态双质子转移(ESDPT)。2002年提出了ESDPT的协调和逐步机制。在协同机制中,两个质子在激发态势能面上一致转移,而局域最小值不存在。另一方面,在分步机制中存在一个中间态。因此,在一个单质子转移后,第二个单质子通过中间态转移。为了确定7ai2的ESDPT机理,进行了大量的光谱和理论研究。本文综述了气相ESDPT的机理。对协调一致的、逐步展开的机制争议作了序章和结语。凝聚相的光谱实验和与势能面有关的理论计算对于得出最终结论是重要的。此外,对一些有意义的结果进行了比较讨论。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Prologue and Epilogue of Concerted and Stepwise Controversy of Excited-state Double-proton Transfer in a Model DNA Base Pair
Excited-state double-proton transfer (ESDPT) in the coplanar 7-azaindole dimer (7AI 2 ) has been studied as a model base pair. Concerted and stepwise mechanisms were proposed for ESDPT in 7AI 2 . In the concerted mechanism, two protons transfer concertedly on the excited-state potential energy surfaces where a local minimum does not exist. On the other hand, an intermediate state exists in the stepwise mechanism. Therefore, after one single-proton transfer, the second single-proton transfers via the intermediate state. Numerous spectroscopic and theoretical studies were con-ducted to determine the mechanism of ESDPT of 7AI 2 . This review focuses on the ESDPT mechanisms in the gas phase. A prologue and epilogue of the concerted and stepwise mechanism controversy are presented. Spectroscopic experiments in the condensed phase and theoretical calculations related to the potential energy surfaces are important for deriving a final conclusion. In addition, some significant results are comparatively discussed.
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