  The intrinsic optical properties and peculiarities of the energy structure of
hafnium dioxide largely determine the prospects for applying the latter in new
generation devices of optoelectronics and nanoelectronics. In this work, we
have studied the diffuse reflectance spectra at room temperature for a
nominally pure nanostructured $HfO_2$ powder with a monoclinic crystal
structure and, as well its photoluminescence in the temperature range of 40 -
300 K. We have also estimated the bandgap $E_g$ under the assumption made for
indirect (5.31 eV) and direct (5.61 eV) allowed transitions. We have detected
emission with a 4.2 eV maximum at T < 200 K and conducted an analysis of the
experimental dependencies to evaluate the activation energies of thermal
quenching (140 meV) and enhancement (3 meV) processes. Accounting for both the
temperature behavior of the spectral characteristics and the estimation of the
Huang-Rhys factor S >> 1 has shown that radiative decay of self-trapped
excitons forms the mechanism of the indicated emission. In this case, the
localization is mainly due to the interaction of holes with active vibrational
modes of oxygen atoms in non-equivalent ($O_{3f}$ and $O_{4f}$) crystal
positions. Thorough study of the discussed excitonic effects can advance
development of hafnia-based structures with a controlled optical response.
