Electronic Structure of the X {^ 1sigma^+} Ion Core of CaF Rydberg States Conference Paper uri icon


  • Abstract We use ab-initio calculations to examine the electronic structure of CaF {^+}, making comparison to the available experimental data and effective potential models. An electron-density-difference plot comparing isolated Ca {+ 2} and F {^-} ions with the CaF {^+} ab-initio density shows sd mixing at Ca, and maintenance of near spherical symmetry at F. This unexpected result is interpreted in terms of the electronic states of Ca {^+}. Calculation of the effective charge on F spanning the region of the transition from ionic to dissociating Ca {^+} F {^ 0} locates the transition very near the crossing of the Ca {+ 2} F {^-} and Ca {^+} F {^ 0} curves and additionally determines the width of the ionic-bonding transition region. An accurate non-relativistic long or intermediate range effective potential for the CaF Rydberg electron is obtained by choice of origin at the center of polarizability, with inclusion of …

publication date

  • June 1, 2015