Permanent and transition dipole moments in CaF and CaCl

Permanent and transition dipole moments have been calculated for various st ates of CaF and CaCl by using an effective one-electron variational eigench annel R-matrix approach combined with generalized quantum defect theory. Th e ion core dipole moment has been evaluated ab initio. The calculations rep roduce the existing measurements involving the lowest states of these compo unds to within about 5%. The calculations yield for the first time electron ic one-photon transition moments for excitation of the higher Rydberg serie s members, from the A (2)Pi, C (2)Pi or D (2)Sigma (+) intermediate states. Permanent dipole moments for the higher Rydberg states have also been eval uated. It is found that the dipolar ion core causes an "internal" Stark eff ect to appear, such that certain series are characterized by strong positiv e dipole moments and other series are characterized by strong negative dipo le moments. (C) 2001 American Institute of Physics.