Pressure-Induced Structural Transitions in M_OO₃·<i>x</i>H₂O (<i>x</i> = 1/2, 2) Molybdenum Trioxide Hydrates: A Raman Study

Abstract

The high-pressure behaviors of M(O)O(3).1/2H(2)O and M(O)O(3).2H(2)O have been investigated by Raman spectroscopy in a diamond anvil cell up to 31.3 and 30.3 GPa, respectively. In the pressure range up to around 30 GPa, both M(O)O(3).1/2H(2)O and M(O)O(3).2H(2)O undergo two reversible structural phase transitions. We observed a subtle structural transition due to O-H...O hydrogen bond in M(O)O(3).1/2H(2)O at 3.3 GPa. We found a soft mode phase transition in M(O)O(3).2H(2)O at 6.6 GPa. At higher pressures, a frequency discontinuity shift and appearance of new peaks occurred in both M(O)O(3).1/2H(2)O and M(O)O(3).2H(2)O, indicating that the second phase transition is a first-order transition. The frequency redshift of the O-H stretching bands of M(O)O(3).1/2H(2)O and M(O)O(3).2H(2)O are believed to be related to the enhancement of the O-H...O weak hydrogen bonds under high pressures.