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 mean-square 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=50 shell closure and N approximately 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 beta softness observed before and after N=60.