Abstract
The infra-red fluorescence spectrum of hexafluorocyclobutene induced by multiphoton absorption is analyzed. The emitting species are likely to be highly excited mode-localized vibrational states of extreme motion. They are characterized by a dominant configuration in which the excitation is mainly localized in one anharmonic-stretching normal-mode of motion. Two time scales are experimentally observed for the collisional decay of the temporal fluorescence obtained when two lasers excite the system within a short time delay at two distinct wavelengths. The fluorescence monitored is of short wavelength and is coming from highly excited species. The first laser excites the molecule into mode-localized extreme-motion states. Further excitation is induced by the second pulse but in a combination of bending and deformation motions. Two decay time scales exist because different modes of motion are being excited although the total vibrational energy of the molecule is large and it is in the quasi-continuum.
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