PHOTODISSOCIATION SPECTROSCOPY OF THE $Ca^{+}, Ar_{2}$ COMPLEX
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Date
2000
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Publisher
Ohio State University
Abstract
The weakly bound complex $Ca^{+} -Ar_{2}$ produced by laser ablation in a pulsed nozzle cluster is studied with mass-selected resonance enhanced photodissociation spectroscopy. A short doublet progression. ($\omega^{\prime}_{e} = 82.07 cm^{-1}$) to the blue of the $^{2}D \leftarrow ^{2}S$ atomic transition is assigned to the $D^{2}\Pi_{r}, \leftarrow X^{2}\Sigma^{+}$ system. Spin-orbit splitting ($A=19.67 cm^{-1}$) of the doublets suggests a linear geometry: A peak observed at $13956 cm^{-1}$ is assigned the $C^{2}\Sigma_{r} \leftarrow X^{2}\Sigma^{+}$ system. No systems are detected from the derived atomic transition $^{2}P \leftarrow ^{2}S$ in this complex. Additionally, complexes with more than two rare-gas ligands were probed and showed no sharp structure. M${\oslash}$ller-Plesset second-order perturbation theory was used to determine the $Ca^{+} -Ar_{2}$ bond distances ($r_{e}$) of 3.064 \AA and a dissociation energy $(D_{e})$ for atomization of 4.864 kcal/mol ($Ca^{+} -Ar_{2} \rightarrow Ca^{+} +2Ar$). This calculation included the correlation of the valence and core electron using a generated basis set for calcium and the aug-ccVQZ basis set for the argon atoms, resulting in a total of 271 basis functions for the calculations.
Description
Author Institution: Department of Chemistry, University of Georgia