Open AccessCrystal Structure of BaCa(CO3)2 Alstonite Carbonate and Its Phase Stability upon Compression
Author(s) -
Raquel Chuliá-Jordán,
D. Santamarı́a-Pérez,
J. RuizFuertes,
Alberto Otero-de-la-Roza,
Cătălin Popescu
Publication year - 2021
Publication title -
acs earth and space chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.876
H-Index - 19
ISSN - 2472-3452
DOI - 10.1021/acsearthspacechem.1c00032
Subject(s) - crystallography , monoclinic crystal system , crystal structure , density functional theory , chemistry , ab initio , phase (matter) , diffraction , stacking , ab initio quantum chemistry methods , powder diffraction , materials science , computational chemistry , molecule , physics , organic chemistry , optics
New single-crystal X-ray diffraction experiments and density functional theory (DFT) calculations reveal that the crystal chemistry of the CaO-BaO-CO 2 system is more complex than previously thought. We characterized the BaCa(CO 3 ) 2 alstonite structure at ambient conditions, which differs from the recently reported crystal structure of this mineral in the stacking of the carbonate groups. This structural change entails the existence of different cation coordination environments. The structural behavior of alstonite at high pressures was studied using synchrotron powder X-ray diffraction data and ab initio calculations up to 19 and 50 GPa, respectively. According to the experiments, above 9 GPa, the alstonite structure distorts into a monoclinic C 2 phase derived from the initial trigonal structure. This is consistent with the appearance of imaginary frequencies and geometry relaxation in DFT calculations. Moreover, calculations predict a second phase transition at 24 GPa, which would cause the increase in the coordination number of Ba atoms from 10 to 11 and 12. We determined the equation of state of alstonite ( V 0 = 1608(2) Å 3 , B 0 = 60(3) GPa, B ' 0 = 4.4(8) from experimental data) and analyzed the evolution of the polyhedral units under compression. The crystal chemistry of alstonite was compared to that of other carbonates and the relative stability of all known BaCa(CO 3 ) 2 polymorphs was investigated.