A novel technique, utilizing thin films with protective capping layers deposited onto silicon photodiode substrates, has been developed to accurately determine the optical constants of reactive elements such as the rare earths and transition metals. Depositing protected layers on photodiode substrates has three primary advantages over the study of the transmittance of free-standing films and the angle-dependent reflectance of coatings on mirror substrates. First, it is easy to deposit a thin protective capping layer that prevents oxidation or contamination of the underlying reactive layer. Second, very thin layers of materials that have intrinsically low transmittance can be studied. Third, the optical constants are determined from the bulk properties of the protected layer and are not influenced by reflectance from the top surface that can be affected by oxidation or contamination. These and other benefits of this technique will be discussed, and results for La and Tb will be presented. The determined optical constants are significantly different from the CXRO and other tabulated values. The rare earth (lanthanide) elements with atomic numbers 57-71 have 5d or 4f open shells, and this open shell structure results in transmission windows in the extreme ultraviolet wavelength range >45 nm where materials typically have low transmittance. These transmission windows make possible the fabrication of a new class of multilayer interference coatings, based on rare earth elements, with relatively high peak reflectances and narrow reflectance profiles, both important factors for the imaging of solar and laboratory radiation sources with multilayer telescopes.