Role of lone-pair electron localization in temperature-induced phase transitions in mimetite.

The crystal structure of mimetite Pb5(AsO4)3Cl, a phosphate with apatite structure-type has been investigated in situ at 123, 173, 273, 288, 353 and 393 K. A careful inspection of the diffraction pattern and subsequent structure refinements indicated that mimetite transforms from the monoclinic to the hexagonal polymorph with increasing temperature. At 123 K, a monoclinic superstructure, mimetite-2M, with cell parameters a = 20.4487 (9), b = 7.4362 (2), c = 20.4513 (9) Å, β = 119.953 (6)°, V = 2694.5 (2) Å3 and space group P21 was observed. From 173 to 353 K, the reflections of the supercell were evident only along one direction of the corresponding hexagonal apatite-cell and the structure transforms to the polymorph mimetite-M with space group P21/b and unit-cell parameters a = 10.2378 (3), b = 20.4573 (7), c = 7.4457 (2) Å, β = 120.039 (5)°, V = 1349.96 (9) Å3. Only at higher temperature, i.e. 393 K, does mimetite adopt the hexagonal space group P63/m characteristic of apatite structure-types. The role of the electron lone pairs of Pb atoms in the phase transition was investigated through the analysis of the electron localization function (ELF) calculated based on the DFT-geometry optimized structures of the three polymorphs. The changes in spatial distribution of the 6s2 electron density during the phase transitions were explored by means of the Wannier Function Centres (WFCs) derived from ab initio molecular dynamics trajectories. In the high-temperature hexagonal structure the 6s2 electrons are spherically symmetric relative to the position of Pb atoms. At low temperature the maximum of 6s2 electron density is displaced relative to the position of Pb atom contributing to the polar interaction in the monoclinic polymorphs