We report a high-pressure study of tetragonal scheelite-type CaMoO4 up to 29
GPa. In order to characterize its high-pressure behavior, we have combined
Raman and optical-absorption measurements with density-functional theory
calculations. We have found evidence of a pressure-induced phase transition
near 15 GPa. Experiments and calculations agree in assigning the high-pressure
phase to a monoclinic fergusonite-type structure. The reported results are
consistent with previous powder x-ray-diffraction experiments, but are in
contradiction with the conclusions obtained from earlier Raman measurements,
which support the existence of more than one phase transition in the pressure
range covered by our studies. The observed scheelite-fergusonite transition
induces significant changes in the electronic band gap and phonon spectrum of
CaMoO4. We have determined the pressure evolution of the band gap for the low-
and high-pressure phases as well as the frequencies and pressure dependences of
the Raman-active and infrared-active modes. In addition, based upon
calculations of the phonon dispersion of the scheelite phase, carried out at a
pressure higher than the transition pressure, we propose a possible mechanism
for the reported phase transition. Furthermore, from the calculations we
determined the pressure dependence of the unit-cell parameters and atomic
positions of the different phases and their room-temperature equations of
state. These results are compared with previous experiments showing a very good
agreement. Finally, information on bond compressibility is reported and
correlated with the macroscopic compressibility of CaMoO4. The reported results
are of interest for the many technological applications of this oxide.Comment: 36 pages, 10 figures, 8 table
