ATOMIC PROPERTIES FROM ELECTRONIC STRUCTURE: X 1Σ+ CaF+

Abstract

begin{itemize}_x000d_ item underline{Purpose}: Compare methods of obtaining atoms-in-molecules properties from _x000d_ electronic structure calculations and spectroscopy._x000d_ item underline{Spectroscopic connection}: Rydberg penetrating states and shape resonances see the atoms, non-penetrating states see molecules. Clusters see both._x000d_ item underline{Scope}: Ca and F in CaF+, and by extension, Ca and F in other bonded and non-bonded environments._x000d_ item underline{Converting molecular properties to atomic models}:_x000d_ begin{enumerate}_x000d_ item Two point-localized models_x000d_ begin{itemize}_x000d_ item dipole induction model with integer ionic charges_x000d_ item Hirshfeld local multipole model_x000d_ end{itemize}_x000d_ end{enumerate}_x000d_ item underline{Data used}:_x000d_ begin{enumerate}_x000d_ item CCSD and CCSD(T) ab-initio calculations._x000d_ item Experimental values of $Q_1^2 - eQ_2$, and of dipole polarizability_x000d_ end{enumerate}_x000d_ item underline{Result}:_x000d_ begin{enumerate}_x000d_ item Hirshfeld model connects long range multipole potential to atomic properties, and matches multipoles._x000d_ item Traditional dipole induction matches calc'd $Q_1, Q_2$, expt'l $Q_1^2-eQ_2$, sensible atomic polarizabilities._x000d_ end{enumerate}_x000d_ _x000d_ end{itemize}_x000d_