First evidence of P21/n to P21/c structural transformation in pyroxene-type LiAlGe2O6 under high-pressure conditions

• A new high-pressure phase transition P21/n–P21/c was found for LaAlGe2O6.
• The transition was also followed by micro-Raman spectroscopy.
• The high-pressure polymorph shows a higher bulk modulus.
• The structural evolution of the two symmetries was determined.

The high-pressure behavior of the pyroxene-type compound LiAlGe2O6, the unique representative of a P21/n-pyroxene, was investigated by in-situ X-ray diffraction and Raman spectroscopy on single-crystal samples hydrostatically pressurized in a diamond-anvil cell. The structure was found to undergo a first-order phase transition on compression, with a critical transition at 5.23±0.02 GPa. Together with a strong volume discontinuity of −ΔV/V0=−4.1% the transition shows a remarkable hysteresis loop over at least 0.70 GPa pressure interval. The bulk modulus of the low- and high-pressure polymorphs corresponds to K0=114(1) and 123(2) GPa, respectively, as described by a 2nd order Birch–Murnaghan equation of state. Based on the systematic extinctions the transition was identified as a P21/n-to-P21/c transformation. The mechanism of structural transformation was identified to be controlled by the stereochemistry of the Li atoms at the M2 site, which changes its coordination number from 5 to 6. The formation of new Li–O bonds involves the co-operative folding of Ge2O6-chains, which explains the anisotropy of axial elasticities and the spontaneous strain across the transformation. Simultaneously the distortion correction of AlO6 units associated with the transition further explains the preference of the P21/c structure under pressure.

Detail of the crystal structures of LP-LAG at 3.48 GPa (left) and HP-LAG at 4.51 GPa (right). Li on M2 are green; AlO6 octahedra (Al at M1) are orange; tetrahedra sites in LP-LAG: T1 (yellow) and T2 (blue); tetrahedra sites in HP-LAG: A-chains (yellow), B-chains (blue). Figure optionsDownload as PowerPoint slide