THE ELECTRONIC STRUCTURE OF YbO: RELATIVISTIC LIGAND FIELD CALCULATIONS AND MULTICONFIGURATIONAL DEPERTURBATION ANALYSIS OF FOUR $^{1}\Sigma^{+}(0^{+})$ STATES
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Date
1993
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Ohio State University
Abstract
A simple, zero-free-parameter relativistic ligand field model is shown to predict accurately $(\sim 50 cm^{-1})$ electronic energies of the $f^{13}s$ configuration of YbO. The parameters of model are: $G_{3}(4f.6s)=337 cm^{-1}$, $\zeta(4f)=2914 cm^{-1}$, $B^{2}_{0}(4f^{+})=8740 cm^{-1}$, $B^{2}_{0}(4f^{+})=9220 cm^{-1}$, $B^{4}_{0}(4f)=1993 cm^{-1}$, $B^{4}_{0}(4f^{+})=2293 cm^{-1}$, $B^{6}_{0}(4f^{+})=944 cm^{-1}, B^{6}_{0}(4f^{+})=1215 cm^{-1}.$ A ligand field, integer-charge model provides a basis for an empirical deperturbation of the low lying $^{1}\Sigma^{+}(0^{+})$ states to their diabatic doubly charged $(Yb^{2}+O^{2-})$ and singly charged ionic $(Yb^{+}O^{-})$ potentials. With use of a simple Rittner model for the diabatic curves, the fit of the experimental vibronic terms of three configurations of YbO produces the parameters (in $cm^{-1}$) [FIGURE] In the diabatic limit, $X^{1}\Sigma^{+}$ state is no longer the ground state, but lies 0.94 eV above the (1)0- state of the $f^{13}s$ configuration. This result is in excellent agreement with ab initio pseudopotential $calculation^{1}$, which placed $X^{1}\Sigma^{+}$ state 0.93 eV above $(I)0^{-}$ predicted ground state. The results of deperturbation lead to $\Delta B00(4f/6s)=39 600 cm^{-1}$ for 4f/6s stabilization energy.
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Author Institution: Department of Chemistry, Emory University Atlanta