This work centres around development and applications of the Resonance Ionization Laser Ion Source (RILIS) of the ISOLDE radioactive ion beam facility based at CERN. The RILIS applies step-wise resonance photo-ionization, to achieve an unparalleled degree of element selectivity, without compromising on ion source efficiency. Because of this, it has become the most commonly used ion source at ISOLDE, operating for up to 75% of ISOLDE experiments. In addition to its normal application as an ion source, the RILIS can be exploited as a spectroscopic tool for the study of nuclear ground state and isomer properties, by resolving the influence of nuclear parameters on the atomic energy levels of the ionization scheme. There are two avenues of development by which to widen the applicability of the RILIS: laser ionization scheme development, enabling new or more efficient laser ionized ion beams and the development of new laser-atom interaction regions. New ionization schemes for chromium, tellurium, germanium, mercury and radium have been determined. Additionally, for the first time, the anode cavity of the VADIS, ISOLDE's variant of the FEBIAD type arc discharge ion source was used as the laser-atom interaction region. A new element selective RILIS mode of operation was established, enabling the ISOLDE RILIS to be coupled with molten targets for the first time, increasing the flexibility of ISOLDE operation and opening a direction for future developments. This combined ion source was termed the VADLIS or Versatile Arc Discharge and Laser Ion Source. A combination of the developments presented in this thesis: an improvement of the laser ionization efficiency and the ability to couple the RILIS with molten targets, satisfied the pre-requisites for the long-awaited extension of the laser spectroscopy studies of exotic mercury isotopes. A sudden onset of extreme shape staggering in the neutron deficient mercury isotopes was revealed by optical pumping and laser spectroscopy experiments at ISOLDE in the 1970s and 1980s, with measurements conducted down to 181Hg. Despite this being one of the most remarkable examples of shape coexistence in the nuclear chart, in the intervening decades the cessation point of this odd-even staggering had yet to be unambiguously determined through measurements of nuclear ground state charge radii. This open question was successfully resolved using the ISOLDE RILIS for in-source resonance ionization spectroscopy. The experiment was performed as part of a large collaboration, using the Leuven Windmill system for alpha-detection; direct ion counting with the ISOLTRAP multi-reflection time-of-fight mass spectrometer (MR-ToF MS); and ion beam current measurements using the ISOLDE Faraday cups. The sensitivity of the technique enabled the measurements to be extended down to 177Hg, providing a definitive answer, that the extreme shape staggering stops at 180Hg.In addition to extending the measurements at the neutron deficient end of the mercury isotope chain, the relative mean square charge radii of both 207Hg and 208Hg was determined. This extended the measurements beyond the N = 126 shell closure, enabling the characterization of the "kink" in the trend of the isotope shifts.