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THE PHOTODISSOCIATION CAGE EFFECT IN VAN DER WAALS COMPLEXES: FLUORESCENCE SPECTRA OF $I_{2} B(^{1}E_{0})$ FROM THE HINDERED PHOTODISSOCIATION OF $I_{2}$ Ar AT 488 nm

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Title: THE PHOTODISSOCIATION CAGE EFFECT IN VAN DER WAALS COMPLEXES: FLUORESCENCE SPECTRA OF $I_{2} B(^{1}E_{0})$ FROM THE HINDERED PHOTODISSOCIATION OF $I_{2}$ Ar AT 488 nm
Creators: Cross, J. B.; Valentini, J. J.
Issue Date: 1982
Abstract: The $B \rightarrow X$ fluorescence of $I_{2}$ produced in the hindered photodissociation of $I_{2}$ Ar at 488 nm has been resolved. The spectra show several vibrational progressions with low rotational energy, the most prominent of these is a $($\upsilon', D)$ progression extending from $\upsilon'=49$ to at least $\upsilon'=23$. The $I_{2}$ Ar complexes were excited and the $I_{2}$ fluorescence was observed under collisionfree conditions in a supersonic free-jet expansion. We attribute these observations to a one atom photodissociation cage effect in the $I_{2}$ Ar complex, in which the molecular iodine, although excited more than $400 cm^{-1}$ above the B state dissociation limit, is prevented from dissociating by energy transfer to the argon atom, resulting in the breaking of the van der Waals bond, $I_{2} Ar\stackrel{488 nm}{\longrightarrow}, I_{2} (B) + Ar,$ leaving the iodine molecule in a bound level of the B electronic state, $386 cm^{-1}$ to $1889 cm^{-1}$ below the dissociation limit. Interpretation of the dynamics of the cage effect in terms of a simple impulsive energy transfer model will be presented.
URI: http://hdl.handle.net/1811/28989
Other Identifiers: 1982-TC'-5
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