TY - JOUR

T1 - New High-Pressure Structures of Transition Metal Carbonates with O3C–CO3 Orthooxalate Groups

AU - Sagatov, Nursultan E.

AU - Sagatova, Dinara N.

AU - Gavryushkin, Pavel N.

AU - Litasov, Konstantin D.

N1 - This research was funded by the RFBR under research project no. 20-03-00774 and the state assignment of the IGM SB RAS. Публикация для корректировки.

PY - 2023/2

Y1 - 2023/2

N2 - Based on the density functional theory and crystal structure prediction approaches, we found a novel high-pressure structure of Fe (Formula presented.) CO (Formula presented.) - (Formula presented.). It is characterized by the presence of ethane-like O (Formula presented.) C–CO (Formula presented.) groups or so-called orthooxalate groups. The formation of such O (Formula presented.) C–CO (Formula presented.) groups has been proposed earlier in melts and aqueous carbonate solutions, but no such examples were known in inorganic crystalline materials. We found that this structure is dynamically and thermally stable at pressures of 50 GPa. Similar structures were also predicted to be dynamically stable for Mn (Formula presented.) CO (Formula presented.), Ni (Formula presented.) CO (Formula presented.), and Co (Formula presented.) CO (Formula presented.). In addition, FeCO (Formula presented.) was found to transform into a similar structure with O (Formula presented.) C–CO (Formula presented.) orthooxalate groups at a pressure above 275 GPa. Additionally, for the first time, we describe the self-diffusion of metal atoms in carbonates at high pressure and at high temperatures. The prediction of novel carbonate structures extends the crystal chemistry of inorganic carbonates beyond the established ones with [CO (Formula presented.)] triangles, [C (Formula presented.) O (Formula presented.)] pyro-groups, and [CO (Formula presented.)] tetrahedra.

AB - Based on the density functional theory and crystal structure prediction approaches, we found a novel high-pressure structure of Fe (Formula presented.) CO (Formula presented.) - (Formula presented.). It is characterized by the presence of ethane-like O (Formula presented.) C–CO (Formula presented.) groups or so-called orthooxalate groups. The formation of such O (Formula presented.) C–CO (Formula presented.) groups has been proposed earlier in melts and aqueous carbonate solutions, but no such examples were known in inorganic crystalline materials. We found that this structure is dynamically and thermally stable at pressures of 50 GPa. Similar structures were also predicted to be dynamically stable for Mn (Formula presented.) CO (Formula presented.), Ni (Formula presented.) CO (Formula presented.), and Co (Formula presented.) CO (Formula presented.). In addition, FeCO (Formula presented.) was found to transform into a similar structure with O (Formula presented.) C–CO (Formula presented.) orthooxalate groups at a pressure above 275 GPa. Additionally, for the first time, we describe the self-diffusion of metal atoms in carbonates at high pressure and at high temperatures. The prediction of novel carbonate structures extends the crystal chemistry of inorganic carbonates beyond the established ones with [CO (Formula presented.)] triangles, [C (Formula presented.) O (Formula presented.)] pyro-groups, and [CO (Formula presented.)] tetrahedra.

KW - crystal structure prediction

KW - density functional theory

KW - high pressure

KW - orthocarbonates

KW - siderite

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85149269261&origin=inward&txGid=6551e4d9668b1cf8b844625f1812b21f

UR - https://www.mendeley.com/catalogue/f4bdc53e-0629-3bcf-b374-e8b09f0464bd/

U2 - 10.3390/sym15020421

DO - 10.3390/sym15020421

M3 - Article

VL - 15

JO - Symmetry

JF - Symmetry

SN - 2073-8994

IS - 2

M1 - 421

ER -