Revealing the role of excited state proton transfer (ESPT) in excited state hydrogen transfer (ESHT): systematic study in phenol–(NH3)n clusters

Abstract

Excited State Hydrogen Transfer (ESHT), proposed at the end of the 20th century by the corresponding authors, has been observed in many neutral or protonated molecules and become a new paradigm to understand excited state dynamics/photochemistry of aromatic molecules. For example, a significant number of photoinduced proton-transfer reactions from X–H bonds have been re-defined as ESHT, including those of phenol, indole, tryptophan, aromatic amino acid cations and so on. Photo-protection mechanisms of biomolecules, such as isolated nucleic acids of DNA, are also discussed in terms of ESHT. Therefore, a systematic and up-to-date description of ESHT mechanism is important for researchers in chemistry, biology and related fields. In this review, we will present a general model of ESHT which unifies the excited state proton transfer (ESPT) and the ESHT mechanisms and reveals the hidden role of ESPT in controlling the reaction rate of ESHT. For this purpose, we give an overview of experimental and theoretical work on the excited state dynamics of phenol–(NH₃)_n clusters and related molecular systems. The dynamics has a significant dependence on the number of solvent molecules in the molecular cluster. Three-color picosecond time-resolved IR/near IR spectroscopy has revealed that ESHT becomes an electron transfer followed by a proton transfer in highly solvated clusters. The systematic change from ESHT to decoupled electron/proton transfer according to the number of solvent molecules is rationalized by a general model of ESHT including the role of ESPT.