CHARGE STABILIZATION OF EXCTIED ELECTRONIC STATES OF $CN^{-}$

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1988

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Ohio State University

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On excitation with energetic particles or VUV radiation. alkali halide crystals doped with $CN^{-}$ display an ultraviolet spectrum which has been attributed1 to emission from an excited triplct state of $CM^{-}$ to $^{1}\Sigma^{+}$ the ground state. This is despite the fact that there are expected to be no bound excited electronic states of $CM^{-}$ hi vocuo. Although this metattable $(\tau - 100 ms.)$ species has previously been labeled $^{3}\Pi$ in anology with CO, there is some evidence it may be $^{3}\Sigma^{+}$ at in $N_{2}$. We have computed the energies and spectroscopic properties of excited electronic states of $CN^{-}$ stabilized by counterion lattices, employing an ab initio MCSCF approach. Results will be presented both for the ground $^{1}\Sigma^{+}$ state and for the low-lying $^{3}\Pi$ and $^{3}\Sigma^{+}$ states. These may be directly compared with experiment. We will also discuss the accuracies of differing countercharge modle for simulating the effets of the lattice.

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$^{1}$ M. Meodenhail aol. chem. phys Letters(submitted).
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