Abstract
Abstract Pulsed field ionization-zero kinetic energy photoelectron spectroscopy has been applied to 1,2,4,5-tetrafluorobenzene in a supersonic jet. The spectrum measured by selecting a specific vibronic level of the butterfly vibrational mode in S 1 by the first laser shows a well-resolved vibrational structure of the cation. A long progression has been assigned to the out-of-plane butterfly vibrational mode 11 with an even quantum number in the cation. From the harmonisity and Franck–Condon factor, it has been concluded that the molecular structure of the tetrafluorobenzene cation is flat, though that in S 1 is non-planer along the butterfly vibrational mode. The geometrical change upon ionization is discussed in terms of the electronic structure.
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