A new method of optical pumping in an ion beam cooler buncher has been developed to selectively enhance ionic metastable state populations. The technique permits the study of elements previously inaccessible to laser spectroscopy and has been applied here to the study of Nb. Model independent meansquare charge radii and nuclear moments have been studied for 90;90 m;91;91 m;92;93;99;101;103 Nb to cover the region of the N ¼ 50 shell closure and N % 60 sudden onset of deformation. The increase in mean-square charge radius is observed to be less than that for Y, with a substantial degree of softness observed before and after N ¼ 60. Collinear laser spectroscopy has for many years been used to provide the (sole) model-independent probe of charge distributions of radioactive nuclei [1]. Efficient optical measurements are typically limited to transitions from atomic (or ionic) ground states or naturally populated low-lying metastable states. However, elements around Z ¼ 40 such as Y, Nb, and Mo present a variety of challenges to such spectroscopic approaches. In this Letter, we report a new, general technique of wide applicability, in which radio ions are deliberately prepared in metastable states by a rapid and efficient method of optical pumping. The technique is exploited here in the spectroscopic study of the A ¼ 100 region.The well-known onset of deformation in the neutronrich A % 100 region has been of long standing interest and the subject of recent mass [2,3], -ray spectroscopic [4,5], and optical measurements [6,7]. Collinear laser spectroscopy of Y isotopes was recently performed [6] in order to extract quadrupole moments in the region for comparison with charge-radii systematics. It was seen that with increasing neutron number from the N ¼ 50 shell closure, the nuclear deformation becomes increasingly oblate and increasingly soft. At N ¼ 60, the transition to a strongly deformed rigid prolate shape occurs, but prior to this, although the nuclear deformation is increasing with N, a proportionate increase in softness is also observed. Mass measurements [2,3] have indicated that the shape change, which is most pronounced for 39 Y, weakens with increasing Z, becoming almost undetectable in the 42 Mo chain. Further detailed model-independent optical analysis of the mean-square charge radii, nuclear moments and values of spin has so far, however, been impossible in the region because of experimental atomic physics constraints.Production of radioactive beams in this region, which are of a refractory nature, is presently limited to relatively small yields, and efficient spectroscopy is therefore required. Such elements are produced for optical study at the JYFL IGISOL facility, University of Jyväskylä, Finland [8]. Following mass selection at this on-line separator, the emittance of the ion beam is reduced in an ion beam cooler [7], which is a gas-filled rf quadrupole, held at a potential just below the $30 kV of the ion source. If desired, a trapping potential can accumulate the ions at the end of the device for ...