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- W2024563935 abstract "The three-photon ionization pathways of phenol involving the S2 electronic state as well as higher molecular resonances are explored. Photoelectron spectra are obtained upon ionization with femtosecond laser pulses at 206 and 412 nm. In addition to the well-known two-photon ionization signal, there is a small component in the spectrum that stems from a three-photon pathway. This path is resonant with the both the S2 state and a superexcited state at 9 eV. The dependence of the three-photon pathway on the laser polarization suggests that the optically bright superexcited state has the same symmetry as the S2 state. Upon two-photon excitation of the superexcited state, a nonradiative decay leads to the population of a set of Rydberg states, which can be ionized by a third laser photon. Photoelectron spectra taken with a time delay between the fourth-harmonic pulse, which prepares the molecule in the S2 state, and the second-harmonic pulse, which ionizes the molecule via the superexcited states, reflect the internal conversion dynamics of S2 to S1. We also observe a component of the three-photon ionization signal that persists beyond the decay time of the S2 state, which suggests that a separate ionization path becomes accessible after the internal conversion to S1. This path may involve another recently discovered valence state with an energy of 7.5 eV. The effect of this latter ionization pathway on the interpretation of time-resolved multiphoton ionization experiments is discussed." @default.
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- W2024563935 date "2001-03-21" @default.
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- W2024563935 title "Ultrafast Dynamics in the Three-Photon, Double-Resonance Ionization of Phenol via the S<sub>2</sub> Electronic State" @default.
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- W2024563935 doi "https://doi.org/10.1021/jp003304g" @default.
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