HELIUM CLUSTER ISOLATION SPECTROSCOPY OF ALKALI DIMERS IN THE TRIPLETMANIFOLD

Helium cluster isolation spectroscopy is a recently developed spectros copic method that involves the formation of a beam of large helium clu sters (10(4) atoms pel-cluster), the capture by the clusters of the at oms or molecules of interest in a law-pressure pick-up cell, and the s pectroscopic study of the isolated species. Here we exploit the unique feature of this method of allowing the selective preparation of high- spin molecular species (e.g., triplet dimers) over their low-spin (sin glet) counterparts to measure the spectra of several alkali dimers in their triplet manifold. By probing via laser-induced fluorescence thei r lowest triplet-to-triplet transitions, Li-2, Na-2, K-2, and NaK are found to reside on the surface of the helium clusters. Since the spect roscopic shifts induced by the helium cluster are minimal, vibrational analysis of the electronic transitions produces transition frequencie s that can be compared to previous ab initio and experimental values. Both bound-bound and bound-free transitions have been observed. Emissi on spectra reveal the presence of vibrational relaxation and nonadiaba tic intersystem crossings of the excited dimers that result from the p roximity of the helium cluster surface. Through this study we improve our understanding of triplet alkali dimer potential energy curves, we test an efficient analytical model to represent them, and we provide i nput information for the study of nonadditive effects present in quart et (spin-polarized) alkali trimers which can be formed using the same method.