Abstract
In solution phase, the solute can be photo-ionized in the lower excitation energy than its ionization potential in gas phase. Therefore, the specific interaction is expected to be exist between the surrounding media and higher excited (Sn) state of the solute. In order to elucidate such polarization effect of solvent on the photoionization process, femtosecond double-pulse excitation was applied to direct detection of low-energy photoionization dynamics of a phenylenediamine derivative in solution phase. From the results of the transient absorption change, in polar solvent, it is clearly indicated that photoionization does not proceed directly from the Sn state, but through specific intermediate state. Moreover,
Highlights
Photoionization is one of the simplest and most important primary processes in photochemical reactions
In order to fully elucidate the real-time dynamics and mechanism of the ejection of electron from the solute surrounded by solvent molecules, we have conducted femtosecond transient absorption measurements under the sequential twophoton excitation condition
TMPD decreases in the shorter wavelength region than 280 nm but it keeps an almost constant value in n-hexane. These results strongly suggest that photoionization effectively takes place through higher excited states in polar acetonitrile and ethanol solution
Summary
Photoionization is one of the simplest and most important primary processes in photochemical reactions. Stabilization of cation and ejected electron by the solvation has been conventionally considered to induce the ionization in the solution phase with the excitation energy lower than the ionization potential in the gas phase [1,2]. In order to fully elucidate the real-time dynamics and mechanism of the ejection of electron from the solute surrounded by solvent molecules, we have conducted femtosecond transient absorption measurements under the sequential twophoton excitation condition.
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