An experimental program has been started to study polymorphic phase transitions under pressure in organic solids using the Be gasketing technique developed by us. This allows us to obtain x-ray diffraction patterns of low symmetry organic solids with high resolution, employing CuK_α radiation. The first organic solid studied is α-resorcinol. At 0.5 GPa, it transforms to its high temperature and denser modification, β-resorcinol. The transformation mechanism is discussed with the help of molecular packing calculations.

X-ray diffraction experiments onp-dichlorobenzene at high pressures show a transition at ∼ 0.3 GPa, to a new phase, the diffraction pattern of which cannot be indexed on the anticipated low temperature monoclinic crystal structure. We have instead found an orthorhombic cell, very closely related to the low temperature monoclinic cell, for this new phase. This structure, which also occurs inp-diiodobenzene at ambient conditions, has cell constantsa =14.02,b = 6.06,c = 7.41Å andZ = 4. The space group is Pbca. This new phase has a non-β herring-bone structure, in contrast with the initialα phase which has aβ-structure with ribbon-like arrangement of molecules, with Cl-Cl contacts of ∼ 4A between adjacent molecules. This implies that with pressure the halogen-halogen interaction in this compound plays a less dominant role in crystal engineering.

AlPO₄ has been compressed to pressures of 16 GPa in a diamond anvil cell and its X-ray diffraction pattern studied by the energy-dispersive technique. The compound is observed to become amorphous at ∼ 12 GPa. This explains the loss of Raman spectrum of AlPO₄ reported by Jayaraman and coworkers (1987).

Recent X-ray diffraction studies on α-quartz (SiO₂) by Kingmaet al [1], have shown the occurrence of a reversible, crystalline-to-crystalline, phase transition just prior to amorphization at ≈ 21 GPa. This precursor transition has also been confirmed by our recent molecular dynamics simulation study [2]. In order to investigate the possibility of a similar behaviour in other isostructural compounds, which also undergo pressure induced amorphization, α-GeO₂ and α-AlPO₄ (berlinite form) were studied using energy dispersive X-ray diffraction. In either of these materials, no such phase transition is detected prior to amorphization. The onset of amorphization and its reversal is found to be time dependent in GeO₂.

High pressure behaviour of FePO₄ in berlinite form has been investigated up to 10 GPa using vibrational Raman spectroscopy and energy dispersive x-ray diffraction. Combination of these techniques along with studies on pressure quenched samples reveal structural transitions in this material from its room pressure trigonal phase to a disordered and a crystalline phase near 3±0.5 GPa. The latter is the Cmcm phase which is the equilibrium structure at high pressures. These high pressure phases do not revert back to its initial structure after release of pressure. Irreversibility of these transformations indicates that FeO₄ tetrahedra do not regain their initial coordination. These high pressure transitions can be rationalized in terms of the three level free energy diagram for such systems.

Infrared absorption and Raman study ofβ-Ni(OH)₂ has been carried out up to 25 GPa and 33 GPa, respectively. The frequency ofA_2u internal antisymmetric stretching O-H mode decreases linearly with pressure at a rate of −0.7 cm⁻1/GPa. The FWHM of this mode increases continuously with pressure and reaches a value of ∼ 120 cm⁻¹ around 25 GPa. There was no discernible change observed in the frequency and width of the symmetric stretchingA_1g O-H Raman mode up to 33 GPa. The constancy of the Raman mode is taken as a signature of the repulsion produced by H-H contacts in this material under pressure. Lack of any discontinuity in these modes suggests that there is no phase transition in this material in the measured pressure range.

By subjecting materials to high pressures one can significantly reduce interatomic and intermolecular distances. This causes drastic changes in the nature of electronic and vibrational states and also in bonding, bringing about several unusual structural, electronic and magnetic phase transitions. In addition, these studies provide a very useful data about the equation of state of the materials of interest. Several examples from our work are presented which elucidate the richness of physics under these conditions.