DYNAMICS OF LINEAR AND T-SHAPED $ArI_{2}$ DISSOCIATION UPON $B \leftarrow X$ EXCITATION: A DISPERSED INTRACAVITY LASER-INDUCED FLUORESCENCE STUDY
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Date
1999
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Publisher
Ohio State University
Abstract
We have recorded the dispersed fluorescence spectra of the linear and the previously well-studied T-shaped isomeric $ArI_{2}$ complexes following $B \leftarrow X$ excitation. The dispersed fluorescence features originate from the free $I_{2} B \rightarrow X$ emission and reveal the $I_{2}$ product vibrational state distribution. The vibrational distribution of photofragment $I_{2}(B)$ produced from dissociation of the T-shaped isomer shows a sharp Poisson distribution, beginning with $\Delta v^{\prime}=-3$ which is nearly independent of excitation energy. The vibrational distribution of $I_{2}(B)$ from the linear isomer is quite different. For excitation energies greater than that corresponding to $I_{2} (B,v^{\prime}=22)$, the product distribution is quite similar to that observed for excitation above the dissociation energy of the B state, i.e., it shows a broad, nearly gaussian distribution of $I_{2}(B)$ vibrational states, well below the excitation energy. For excitation energies below that, the distribution becomes increasingly like the Poisson distribution observed for the T-shaped isomer. Bond dissociation energies for linear and T-shaped isomers are determined for the spectra. The dissociation time scale for the two isomers differs by about 3 orders of magnitude. To model the product state distribution of the linear isomer and therefore gain further insight into the $Ar-I_{2}$ interaction potential, a simple trajectory calculation based upon the classical dynamics of a compressed oscillator (I-I) ejecting a freely attached particle (Ar) is in progress. Results from the calculation are in good accord with the experiment.
Description
Author Institution: Department of Chemistry, Harvard University