TY - JOUR

T1 - Metastable structures of CaCO3and their role in transformation of calcite to aragonite and postaragonite

AU - Gavryushkin, Pavel N.

AU - Belonoshko, Anatoly B.

AU - Sagatov, Nursultan

AU - Sagatova, Dinara

AU - Zhitova, Elena

AU - Krzhizhanovskaya, Maria G.

AU - Recnik, Aleksander

AU - Alexandrov, Eugeny V.

AU - Medrish, Inna V.

AU - Popov, Zakhar I.

AU - Litasov, Konstantin D.

N1 - Funding Information: This study was funded by the RFBR under research project #18-35-20047. Some of the analyses of high-pressure metastable modifications were also supported by a state-assigned project of the IGM SB RAS. TEM studies were conducted under bilateral project BI-RS/18-19-026 supported by the Slovenian Research Agency. A.B.B. was supported by the Swedish Scientific Council research grant “Mineral Physics of the Earth’s Core”. A.B.B. also acknowledges HSE support. E.V.A. thanks the Ministry of Education and Science of the Russian Federation for their financial support under grant no. 0778-2020-0005. Z.I.P. acknowledges financial support by the Ministry of Science and Higher Education of the Russian Federation (project 01201253304). The computations were performed using resources provided by the Novosibirsk State University Supercomputer Center and by SNIC through the National Supercomputer Center at Linköping Technical University (Sweden). The XRPD experiments were carried out using facilities at the XRD Resource Center of St. Petersburg State University. Publisher Copyright: © 2020 American Chemical Society. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2021/1/6

Y1 - 2021/1/6

N2 - Using molecular dynamics simulation and evolutionary metadynamic calculations, a series of structures were revealed that possessed enthalpies and Gibbs energies lower than those of aragonite but higher than those of calcite. The structures are polytypes of calcite, differing in the stacking sequence of close-packed (cp) Ca layers. The two- and six-layered polytypes have hexagonal symmetry P6322 and were named hexarag and hexite, respectively. Hexarag is similar to aragonite, but with all the triangles placed on the middle distance between the cp layers. On the basis of the structures found, a two-step mechanism for the transformation of aragonite to calcite is suggested. In the first step, CO3 triangles migrate to halfway between the Ca layers with the formation of hexarag. In the second step, the two-layered cp (hcp) hexarag structure transforms into three-layered cp (fcc) calcite through a series of many-layered polytypes. The topotactic character of the transformation of aragonite to calcite, with [001] of aragonite being parallel to [0001] of calcite, is consistent with the suggested mechanism. High-temperature X-ray powder diffraction experiments did not reveal hexarag reflections. To assess the possibility of the formation of the polytypes found in nature or experiments, a TEM analysis of ground aragonite was performed. A grain was found that had six superstructure reflections in a direction perpendicular to the plane of the cp layer. This grain is believed to correspond to one of the predicted polytypes, with the diffuse character of the diffraction spots indicating a partial disordering of the cp layer stacking. A topological analysis was also performed, along with energy calculations, of the metastable high-pressure polymorphs CaCO3-II, -III, -IIIb, and -VI. The similarity of CaCO3-II, -II, and -IIIb to the calcite structure and the small energy difference explain the metastable formation of these polymorphs during the cold compression of calcite. On the basis of the performed analysis, the evolution of the CaCO3 cation array at calcite to a post-aragonite transformation is described.

AB - Using molecular dynamics simulation and evolutionary metadynamic calculations, a series of structures were revealed that possessed enthalpies and Gibbs energies lower than those of aragonite but higher than those of calcite. The structures are polytypes of calcite, differing in the stacking sequence of close-packed (cp) Ca layers. The two- and six-layered polytypes have hexagonal symmetry P6322 and were named hexarag and hexite, respectively. Hexarag is similar to aragonite, but with all the triangles placed on the middle distance between the cp layers. On the basis of the structures found, a two-step mechanism for the transformation of aragonite to calcite is suggested. In the first step, CO3 triangles migrate to halfway between the Ca layers with the formation of hexarag. In the second step, the two-layered cp (hcp) hexarag structure transforms into three-layered cp (fcc) calcite through a series of many-layered polytypes. The topotactic character of the transformation of aragonite to calcite, with [001] of aragonite being parallel to [0001] of calcite, is consistent with the suggested mechanism. High-temperature X-ray powder diffraction experiments did not reveal hexarag reflections. To assess the possibility of the formation of the polytypes found in nature or experiments, a TEM analysis of ground aragonite was performed. A grain was found that had six superstructure reflections in a direction perpendicular to the plane of the cp layer. This grain is believed to correspond to one of the predicted polytypes, with the diffuse character of the diffraction spots indicating a partial disordering of the cp layer stacking. A topological analysis was also performed, along with energy calculations, of the metastable high-pressure polymorphs CaCO3-II, -III, -IIIb, and -VI. The similarity of CaCO3-II, -II, and -IIIb to the calcite structure and the small energy difference explain the metastable formation of these polymorphs during the cold compression of calcite. On the basis of the performed analysis, the evolution of the CaCO3 cation array at calcite to a post-aragonite transformation is described.

KW - CRYSTAL-STRUCTURE PREDICTION

KW - TOTAL-ENERGY CALCULATIONS

KW - HIGH-PRESSURE POLYMORPHS

KW - X-RAY-DIFFRACTION

KW - PHASE-TRANSITIONS

KW - IN-SITU

KW - MICROSTRUCTURES

KW - MECHANISM

KW - STATE

UR - http://www.scopus.com/inward/record.url?scp=85098763726&partnerID=8YFLogxK

U2 - 10.1021/acs.cgd.0c00589

DO - 10.1021/acs.cgd.0c00589

M3 - Article

AN - SCOPUS:85098763726

VL - 21

SP - 65

EP - 74

JO - Crystal Growth and Design

JF - Crystal Growth and Design

SN - 1528-7483

IS - 1

ER -