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- W2018856466 abstract "The 7-azaindole dimer (7AI 2 ) is a prototype of double hydrogen-bonded molecules. 7AI 2 has been considered as a model DNA base pair and has attracted much attention to the mechanism of the excited-state double-proton transfer (ESDPT). Two ESDPT mechanisms, stepwise and concerted mechanisms, have been proposed so far. Great efforts have been devoted to clarify the mechanism of ESDPT using experimental and theoretical methods. However, the reaction mechanism had been controversial for more than a decade. We provide the resolution of the two mechanisms on the basis of new data obtained from electronic spectroscopy and picosecond time-resolved spectroscopy in the gas phase. The initial state of the ESDPT reaction has been well characterized by investigating the exciton resonance interaction with UV-UV hole-burning spectroscopy for various 7AI 2 isotopomers. The lowest-excited state of 7AI 2 has been classified into the weak coupling case of the exciton theory. We have concluded that the ESDPT reaction in 7AI 2 occurs via the concerted mechanism on the basis of the results of picosecond time-resolved experiments and the H/D kinetic isotope effect on ESDPT studied by measuring the vibronic-state selective dispersed fluorescence spectra. ESDPT of 7AI 2 has a dynamic cooperative nature that may arise from the coupling of the two moving protons with the reorganization of electrons. We have provided a new paradigm of ESDPT, where two quantum effects, the exciton resonance interaction and the proton tunneling, are concerned with the ESDPT reaction." @default.
- W2018856466 created "2016-06-24" @default.
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- W2018856466 date "2006-03-01" @default.
- W2018856466 modified "2023-10-10" @default.
- W2018856466 title "Excited-State Double-Proton Transfer in the 7-Azaindole Dimer in the Gas Phase. Resolution of the Stepwise versus Concerted Mechanism Controversy and a New Paradigm" @default.
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- W2018856466 doi "https://doi.org/10.1246/bcsj.79.373" @default.
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