The electronic structure of the calcium monohalides. A ligand field approach

Abstract

The electronic structure of the calcium monohalides is addressed using a ligand field model which approximates the halide as a polarizable negative charge perturbing the one electron valence structure of the Ca+ ion. A simple, zero-free-parameter model is shown to predict accurately electronic energies, transition moments, permanent dipole moments, and several other molecular constants that have been experimentally determined. The molecular properties and electronic wave functions are interpreted in terms of the polarization (s/p/d/f mixing) and radial expansion (nl/n+1l mixing) of the low lying, free ion, basis functions caused by the electric field of the ligand.

Simulations of the bichromatic force in multilevel systems

“…The decay branching ratios to different electronic states scale as |d ij | 2 ν 3 ij . The dipole transition moments have been estimated via ligand field modeling [32] and the transition frequencies are known [33], so the ratio of decay rates to the can be estimated:…”

Direct detection of Rydberg–Rydberg millimeter-wave transitions in a buffer gas cooled molecular beam

“…[6,[13][14][15] To study the structure and dynamics of the molecular Rydberg states with both high resolution and a fast data acquisition rate, we incorporate two cru- (ii) The BaF molecular beam generated from our buffer gas cooled ablation source is a factor of 1000 brighter and has 10 times slower laboratory frame velocity than a BaF beam generated by our Smalley-type supersonic jet ablation source. Exploitation of the broad bandwidth, multiplexed, FID-detection scheme would have been impractical without the enhanced brightness of the buffer gas cooled ablation source.…”

Theoretical study on analytical potential function and spectroscopic parameters for CaF molecule

“…In addition, they are good candidates for comprehensive laser spectroscopic studies [9,10] because the ionization potentials of their Rydberg series are relatively low (, 5 -6 eV). The ground state and the valence excited A, B, and C states of these molecules were described by Rice et al [5] using a ligand-field model and by Törring et al [6] using an electrostatic polarization model. d'Incan et al [11,12] experimentally observed some excited states of CaF.…”