Quantum defect theory of dipole-mixed Rydberg states in CaF

491 rovibronic levels of electronically highly excited CaF have been analyz ed using multichannel quantum defect theory (MQDT). These levels, observed in the experiments described in the preceding paper, correspond to effectiv e principal quantum numbers v approximate to 12-18, partial wave components l = 0-3, and vibration-rotation quantum numbers v = 1 and N = 0-14. A set of nondiagonal quantum defect matrices has been extracted from the experime ntal data by means of a global least-squares-fitting procedure, and is foun d to agree reasonably well with the theoretical quantum defect matrices cal culated previously by Arif et al. J. Chem. Phys. 106, 4102 (1997) where the variational R-matrix method was used. The MQDT analysis accounts for rotat ional-electronic nonadiabatic decoupling of the Rydberg electron from the r otating dipolar core as well as for strong l-mixing induced by the latter. The quantum defects determined for l = 3 yield approximate values for the c ore dipole and quadrupole moments.