Crystal behavior of potassium bromate under compression

We report on high-pressure angle-dispersive X-ray diffraction data up to 15 GPa and ab initio total-energy calculations up to 242 GPa for KBrO₃. No phase transition was found below 15 Pa in contrast to previously reported data. Its experimental bulk modulus in the quasi-hydrostatic regime is B₀ = 18.8 (9) GPa with a bulk modulus pressure derivative B′₀ = 8.2 (4). However, according to our ab initio calculations, KBrO₃ significantly reduces its rhombohedral distortion via small cooperative movements of the atoms and the structure progressively approaches the cubic symmetry, where the KBr subarray would adopt a topology similar to that of the corresponding B2-type bromide. This rearrangement of atoms is directly related to the Buerger's mechanism of the B1–B2 phase transition for halides, confirming that cations (second neighbors) do not arrange in an arbitrary way. The O atoms forming the [BrO₃] pyramidal units move smoothly with pressure to the center of the [K₈] cube faces, where electron localization function calculations present their maxima in other B2-type compounds, eventually adopting the perovskite-type structure at P ≃ 152 GPa. Our data on KBrO₃ has been compared with chemically substituted isostructural halates, providing new insights on the compressibility of this family of compounds.

Computing details

Program(s) used to refine structure: FULLPROF.

(I)

Crystal data

KBrO3	Z = 3
Mr = 167	Mo Kα radiation
Trigonal, R3m	T = 295 K
Hall symbol: R 3 -2"	white
a = 6.0104 (17) Å	cylinder, 0.5 × 0.5 mm
c = 8.162 (4) Å	Specimen preparation: Prepared at 295 K and 101.3 kPa
V = 255.35 (15) Å^3

Data collection

Xcalibur Oxford Difraction diffractometer	Data collection mode: transmission
Radiation source: sealed X-ray tube	2θmin = 3.975°, 2θmax = 34.645°, 2θstep = 0.024°
Specimen mounting: 0.5-mm glass capillary

Refinement

Rp = 12.697	Profile function: pseudo-Voigt
Rwp = 93.279	10 parameters
Rexp = 35.112	0 restraints
RBragg = 11.630	Background function: 68 background points
1282 data points

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
K	0.00000	0.00000	0.00000	0.039 (19)*
Br	0.00000	0.00000	0.483 (9)	0.023 (10)*
O	0.476 (8)	0.524 (8)	0.068 (11)	0.03 (3)*