PHOTOELECTRON SPECTROSCOPY OF $ClH_{2}^{-}$ AND $ClD_{2}^{-}$: A PROBE OF THE $Cl + H_{2}$ VAN DER WAALS WELL AND SPIN-ORBIT EXCITED STATES
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Date
2003
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Ohio State University
Abstract
The anion photoelectron spectra of $ClH_{2}^{-}$ and $ClD_{2}^{-}$ were measured at 299 nm, accessing the prereactive van der Waals well on the ground state $Cl + H_{2}$ potential energy surface, as well as the low-lying spin-orbit excited states resulting from the interaction of $Cl (^{2}P_{3/2})$ and $Cl^{\ast} (^{2}P_{1/2})$ with $H_{2}$. The photoelectron spectra are dominated by two relatively narrow peaks corresponding to the transitions to the neutral $Cl\cdot H_{2}$ and $Cl^{\ast}\cdot H_{2}$ complexes both are shifted toward higher electron binding energy relative to atomic chlorine due to the solvent shift by the hydrogen. Another feature in the spectra is the relative broadening of $ClD_{2}^{-}$ versus $ClH_{2}^{-}$. The broadening of the $ClD_{2}^{-}$ peaks may have its origins in the excited state transitions. The broadening may also be in part due to the presence of two nuclear spin species, as opposed to one in $ClH_{2}^{-}$. Only $ClH_{2}^{-}$ (ortho) was generated in this experiment, while $ClD_{2}^{-}$ had both ortho and para complexes generated.
Description
Author Institution: Department of Chemistry, University of California; Chemical Sciences Division, Lawrence Berkeley National Laboratory