The Predissociation Mechanism for 2Sigma+ Rydberg States of CaCl

This work summarizes experimental results from recent ion-dip spectroscopy studies of CaCl and from previously unpublished optical-optical double-resonance work with specific regard to predissociation processes of 2Sigma+ Rydberg states in the low n* (n* = 7, IP - En* = 2240 cm-1) region. A single repulsive state (assigned as 2Sigma+) was found to be responsible for all observed predissociations of 2Sigma+ Rydberg states. The n*-dependent internuclear distances of the intersections between Rydberg states and the repulsive 2Sigma+ state were determined through the use of trial-and-error Franck-Condon calculations. Values of energy-descaled electronic matrix elements governing the Rydberg left and right arrow repulsive state interaction were obtained from the measured linewidths (0.6 < Gamma < 1.2 cm-1) and computed Franck-Condon densities. Copyright 1999 Academic Press.