Double-Resonance Spectroscopic Studies of Core-Penetrating Rydberg States of CaCl

Six core-penetrating Rydberg series have been assigned in the CaCl molecule by a combination of double-resonance spectroscopic techniques. Two 2Sigma+ series, with approximate quantum defects (delta) of 0.51 and 0.25, have been observed with effective principal quantum numbers (n*) in the range of 5-8 using the D2Sigma+ state as the resonant intermediate state for REMPI and/or ion-dip detection. A third 2Sigma+ series with delta approximately 0.84 and a 2Delta series with delta approximately 0.95 have been observed with n* = 16-18 using the A2Pi3/2 state as the resonant intermediate state for preparation of v+ = 1 vibrationally autoionizing states. Two additional series in the same region with delta approximately 0.90 and 0.07 are tentatively identified as the expected core-penetrating 2Pi series. Vibrational assignments have been confirmed in many cases on the basis of isotope shifts between the 35Cl and 37Cl isotopomers. The ion-dip and REMPI spectra display linewidths systematically broadened by predissociation. In addition to the assigned core-penetrating series, both the REMPI and the ion-dip spectra display some sharper features that have not yet been assigned. These sharper features most likely arise from perturbations of optically "bright" core-penetrating states by nominally "dark" higher-l core-nonpenetrating states. Copyright 1999 Academic Press.