$CL_{3}{^{-}}$ ELECTRON PHOTODETACHMENT SPECTRUM: MEASUREMENT AND ASSIGNMENT

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1999

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Ohio State University

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An electron photodetachment spectrum of $Cl_{3}{^{-}}$ is reported for 193 nm (6.42 eV) excitation. The spectrum was assigned using high-level abinitio calculations for the $Cl_{3}$ radical and the $Cl_{3}{^{-}}$ anion. A broad band centered around 1.25 eV (electron kinetic energy) has been assigned to the $Cl_{3}{^{-}}(X^{1}\Sigma^{+}{_{g}})\to Cl_{3}(X^{2}\Pi_{u})$ and $Cl_{3}(1^{2}\Sigma^{+}{_{g}})$ transitions. Vertical photodetachment accesses the transition state region for the Cl exchange reaction: $Cl+Cl_{2}\longrightarrow Cl_{2}+Cl$. A narrow doublet band at 0.55 eV is assigned to the $Cl_{3}{^{-}}(X^{1}\Sigma^{+}{_{g}})\to Cl_{3}(1^{2}\Pi_{g})$ transition, split by spin-orbit interaction.

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Author Institution: Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University; Department of Chemistry, University of California

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