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OPEN Comparative study

on high‑pressure physical
properties of monoclinic M
­ gCO3
and ­Mg2CO4
Zi‑Jiang Liu1*, Tian Li1, Xiao‑Wei Sun1, Cai‑Rong Zhang2 & Jia‑Qi Ju1
The physical properties of Mg-carbonate at high temperature and pressure are crucial for
understanding the deep carbon cycle. Here, we use first-principles calculations to study the physical
properties of ­MgCO3-C2/m and ­Mg2CO4-P21/c under high pressure. The research shows that the
structure and equation of state of ­MgCO3-C2/m are in good agreement with the experimental results,
and the phase transition pressure of ­Mg2CO4 from pnma to P21/c structure is 44.66 GPa. By comparing
the elastic properties, seismic properties and anisotropy of ­MgCO3-C2/m and ­Mg2CO4-P21/c, it is
found that the elastic modulus and sound velocity of ­Mg2CO4-P21/c are smaller than those of ­MgCO3-
C2/m, while the anisotropy is larger than that of ­MgCO3-C2/m. These results indicate that ­Mg2CO4-
P21/c exists in the deep mantle and may be the main reason why carbonate cannot be detected. The
minimum thermal conductivity of ­MgCO3-C2/m and ­Mg2CO4-P21/c is the largest in the [010] direction
and the smallest in the [001] direction. The thermodynamic properties of ­MgCO3-C2/m and ­Mg2CO4-
P21/c are predicted using the quasi-harmonic approximation (QHA) method.

Magnesite (space group R3c ) is subducted into the deep mantle as the primary carbon carrier, and its high-
temperature and high-pressure physical properties are critical for understanding the deep carbon ­cycle1,2. Previ-
ous studies have mainly focused on the structural phase transition of M ­ gCO3-R3c under high-temperature and
high-pressure conditions, transforming to monoclinic M ­ gCO3 (space group C2/m) at around 80 GPa. Oganov
et al. used the USPEX method to predict for the first time that M ­ gCO3-C2/m is most stable in the lower mantle
greater than 82.4 ­GPa3. ­MgCO3-C2/m has 30 atoms, in which adjacent oxygen atoms form tetrahedra around
carbon atoms, and Mg atoms are in octet and tenfold coordination. Subsequently, the structure of M ­ gCO3-C2/m
was verified ­experimentally4–6 and ­theoretically7–13. Recently, Gavryushkin et al. used USPEX and AIRSS methods
to find that ­MgCO3 reacts with MgO to form ­Mg2CO4, which has two structures, orthorhombic (space group
Pnma) and monoclinic (space group P21/c), and its structure is P21/c when the pressure is higher than 50 ­GPa14.
Their experiments later confirmed the existence of M ­ g2CO4-P21/c at the temperature and pressure of the Earth’s
lower ­mantle15. ­Mg2CO4-P21/c has 28 atoms, it is isostructural to β-Ca2SiO416, and the atoms at the two positions
Mg(1) and Mg(2) are six-coordinated, with octahedral coordination polyhedra. Earlier ­reports17–20, although the
structure of M­ g2CO4 was not determined, believed that it is stable at high pressure.
To understand the carbon cycle in the deep earth, it is crucial to study the structure, phase transition, equa-
tions of state, elasticity, thermodynamics, and thermal conductivity of ­MgCO3-C2/m and M ­ g2CO4-P21/c under
high pressure. Recently, Maeda et al. measured the equation of state of M ­ gCO3-C2/m at high p ­ ressure6. Since
it is extremely difficult to measure the elastic constants, thermodynamic parameters, and thermal conductivity
of minerals experimentally, the properties of M ­ gCO3-C2/m and ­Mg2CO4-P21/c have not been reported experi-
mentally. Even the elastic constant of ­MgCO3-R3c can only be measured to 13.7 ­GPa21, and its thermodynamic
properties are only at low pressure, and the results at high pressure are ­extrapolated22–24.
In the present work, the structures, phase transitions, equations of state, elastic properties, seismic properties,
and minimum thermal conductivity of M ­ gCO3-C2/m and ­Mg2CO4-P21/c at high pressure are investigated using
first-principles calculations and compared with the available experimental and theoretical results. The QHA
method is adopted to research the thermodynamic properties of M ­ gCO3-C2/m and ­Mg2CO4-P21/c.

1
School of Mathematics and Physics, Lanzhou Jiaotong University, Lanzhou 730070, China. 2Department of
Applied Physics, Lanzhou University of Technology, Lanzhou 730050, China. *email: liuzj1024@hotmail.com

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Figure 1.  Crystal structures of ­MgCO3-C2/m (a) and ­Mg2CO4-P21/c (b) in unit cell. The crystal structures are
drawn by ­VESTA32.

Method a (Å) b (Å) c (Å) β V(Å3)

MgCO3-C2/m
This work 8.104 6.493 6.884 103.893 351.61
Binck et al.5 8.117 6.510 6.911 103.858 354.64
Mg2CO4-P21/c
This work 4.383 5.358 8.293 117.56 172.65
Gavryushkin et al.14 4.408 5.383 8.345 117.65 175.39

Table 1.  Lattice parameters of ­MgCO3-C2/m and ­Mg2CO4-P21/c at 110 GPa and 100 GPa, respectively,
compared with experimental and previous calculations.

Methods
First-principles calculations are used to investigate the high-pressure physical properties of ­MgCO3-C2/m and
­Mg2CO4-P21/c using projector-augmented wave (PAW)25 as implemented in ­VASP26,27. The electronic con-
figurations: ­2p63s2 for Mg, 2­ s22p2 for C and 2­ s22p4 for O are considered for the valence electrons. The Per-
dew–Burke–Ernzerhof modified solid (PBEsol) in the generalized gradient approximation (GGA)28 describes
the exchange and correlation potentials. The generation of k-point mesh and the calculation of elastic proper-
­ rogram29. The cutoff energy for the plane wave is set to 900 eV. The k-points mesh of
ties utilize the vaspkit p
­MgCO3-C2/m and M ­ g2CO4-P21/c are set to 4 × 5 × 5 and 13 × 9 × 7 using the Monkhorst–Pack ­scheme30, respec-
tively. The thermodynamic properties are calculated by the QHA ­method31.

Results and discussion

Structural parameters, phase transition and equation of state. The crystal structures of
­MgCO3-C2/m and ­Mg2CO4-P21/c in the unit cell are shown in Fig. 1. The optimized lattice parameters are sum-
marized in Table 1 and compared with available experimental and previously calculated results. At 110 GPa, the
­ gCO3-C2/m are consistent with the experimental r­ esults5. The results for M
calculated results of M ­ g2CO4-P21/c
at 100 GPa agree well with the previous ­calculations14.
As shown in Fig. 2, the present calculated transition pressure from ­Mg2CO4-Pnma to M ­ g2CO4-P21/c is 44.66
GPa, while Gavryushkin et al. calculated 52 ­GPa14. This error may be caused by the use of different exchange
correction functions, PBEsol is used in the present work, while PBE was used by Gavryushkin et al.14. The accu-
racy of using PBEsol to calculate the properties of Mg-carbonate has been examined in the previous s­ tudies13.
In the previous study, ­MgCO3-C2/m was stable in the lower mantle above 80 ­GPa3,5–13,33. Therefore, in order to
facilitate comparison, the high-pressure properties of M ­ gCO3-C2/m and M ­ g2CO4-P21/c in the pressure range
of 50–140 GPa are investigated in this work.
The equations of state for M­ gCO3-C2/m and ­Mg2CO4-P21/c at 50 to 140 GPa are shown in Fig. 3. It is found
that the equation of state of ­MgCO3-C2/m is in good agreement with available experimental ­data6. The equation
of state of M
­ g2CO4-P21/c is smaller than that of M
­ gCO3-C2/m, and is almost parallel. The formula unit volume
of ­MgCO3-C2/m is smaller than that of ­Mg2CO4-P21/c, which is in line with their molecular formula composi-
tion relationship.

Elastic properties. For monoclinic ­MgCO3-C2/m and M ­ g2CO4-P21/c, there are 13 independent elastic con-
stants (c11, c12, c13, c15, c22, c23, c23, c25, c33, c35, c44, c46, c55 and c66). The elastic constants are calculated using the
stress–strain ­method29. In this work, all calculated elastic stiffness constants cij are checked using the mechanical

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Enthalpy difference (eV)

1 44.66 GPa

-1

-2

-3
10 20 30 40 50 60 70 80

Pressure (GPa)

Figure 2.  Enthalpy difference between ­Mg2CO4-P21/c and ­Mg2CO4-Pnma.

450 50
a b

400
45

Formula unit volume (Å3)

350
Unit cell volume (Å3)

40

300
MgCO3-C2/m(exp.) MgCO3-C2/m
MgCO3-C2/m 35
Mg2CO4-P21/c
250 Mg2CO4-P21/c

30
200

150 25
60 80 100 120 140 60 80 100 120 140

Pressure (GPa) Pressure (GPa)

Figure 3.  Equation of state for ­MgCO3-C2/m and ­Mg2CO4-P21/c.

stability ­criteria34 and find that they all meet the mechanical stability criteria in the studied pressure range, thus
they are mechanically stable.
The elastic constants of M ­ gCO3-C2/m and M ­ g2CO4-P21/c are plotted in Figs. 4 and 5, respectively. It is found
from Fig. 4 that at 50–110 GPa, c22 > c33 > c11, indicating that the a-axis of ­MgCO3-C2/m is the most easily
compressed, and the b-axis is the least compressed. At > 110 GPa, c33 > c22 > c11, the c-axis is least likely to be
compressed. From Fig. 5, it can be seen that c22 > c11 > c33 in the studied pressure range, indicating that the
c-axis of M ­ g2CO4-P21/c is the most easily compressed, and the b-axis is the least compressible. In the previous
­study13, the elastic constants of ­MgCO3-R3c are consistent with the experimental ­results21. Therefore, the pre-
dicted elastic constants of ­MgCO3-C2/m and ­Mg2CO4-P21/c in this work should be correct, but it needs to be
further verified by experiments.
Based on the calculated elastic constants, the bulk modulus B and shear modulus G of ­MgCO3-C2/m and
­Mg2CO4-P21/c are calculated using the Voigt-Reuss-Hill m ­ ethod35–37. As shown in Fig. 6, the bulk modulus B and
shear modulus G of M ­ gCO3-C2/m and ­Mg2CO4-P21/c increase with increasing pressure, and the bulk modulus
B and shear modulus G of ­MgCO3-C2/m are larger than those of ­Mg2CO4-P21/c at 50–140 GPa.

Seismic properties. Based on the calculated bulk and shear moduli and density, the compression (VP) and
­ g2CO4-P21/c are given by the following ­expressions38:
shear (VS) velocities of ­MgCO3-C2/m and M

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1200 300

c11 c44
c22 c55
250
1000 c33 c66

Elastic constants (GPa)

200
800

150

600

100
60 80 100 120 140 60 80 100 120 140
600 600

c12 c23
c13 c25
400 c15 c35
Elastic constants (GPa)

400
c46

200

200

0
60 80 100 120 140 60 80 100 120 140

Pressure (GPa) Pressure (GPa)

Figure 4.  Elastic constants of M

­ gCO3-C2/m.

1200 250

c11 c44
c22 c55
1000 c33 200 c66
Elasc constants (GPa)

800 150

600 100

60 80 100 120 140 60 80 100 120 140

600 600

500

400 400
Elasc constants (GPa)

300 c23
c25
c12 200
200 c35
c13
c46
100 c15
0
0

60 80 100 120 140 60 80 100 120 140

Pressure (GPa) Pressure (GPa)

Figure 5.  Elastic constants of M

­ g2CO4-P21/c.

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800
B, MgCO3-C2/M
B, Mg2CO4-P21/c
G, MgCO3-C2/M
600
G, Mg2CO4-P21/c

Elastic modulus (GPa)

400

200

0
60 80 100 120 140

Pressure (GPa)

Figure 6.  Bulk modulus B and shear modulus G of ­MgCO3-C2/m and ­Mg2CO4-P21/c.

5.2

MgCO3-C2/m
5.0 Mg2CO4-P21/c

4.8
Density (g/cm3)

4.6

4.4

4.2

4.0
60 80 100 120 140

Pressure (GPa)

Figure 7.  Density of ­MgCO3-C2/m and ­Mg2CO4-P21/c.


3B + 4G
VP = (1)
3ρ


G
VS = (2)
ρ

As shown in Fig. 7, the density of M ­ g2CO4-P21/c is larger than that of ­MgCO3-C2/m, and the difference
between their bulk modulus and shear modulus is smaller, respectively. Therefore, the VP and VS of M ­ gCO3-C2/m
are larger than those of M ­ g2CO4-P21/c in the studied pressure range, and their VP and VS tend to be parallel,
respectively (See Fig. 8).
The VP and VS of M ­ gCO  3-C2/m and M ­ g2CO  4-P21/c along different directions can be obtained by solving
the Christoffel ­equation39 Cijkl nj nl − ρV 2 δik  = 0 . In order to visualize the propagation wave velocities of
­MgCO3-C2/m and M ­ g2CO4-P21/c along different directions, the AWESoMe p ­ rogram40,41 is used to plot their
3D representations of VP and VS and shear wave splitting and polarization vectors at various pressures (Figs. 9
and 10).
The anisotropy AP of the VP for ­MgCO3-C2/m and ­Mg2CO4-P21/c is defined a­ s42:
VP,max − VP,min
AP =
VP,aggregate
× 100%. (3)

The polarization anisotropy AS of the VS is defined as

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15

VP

12

Wave velocity (km/s)

MgCO3-C2/m
Mg2CO4-P21/c
9

VS
6

60 80 100 120 140

Pressure (GPa)

Figure 8.  Compression (VP) and shear (VS) velocities of M

­ gCO3-C2/m and ­Mg2CO4-P21/c.

Figure 9.  3D representation of the VP and VS and the shear wave splitting and polarization vectors of ­MgCO3-
C2/m at various pressures.

(VS1 − VS2 )max

AS = × 100%. (4)
VS,aggregate

The seismic anisotropies of M

­ gCO3-C2/m and M ­ g2CO4-P21/c are shown in Fig. 11. The seismic anisotropy of
­MgCO3-C2/m at 75 GPa is found to be in good agreement with the previous theoretical c­ alculations10. The ani-
sotropy of ­Mg2CO4-P21/c is obviously larger than that of ­MgCO3-C2/m. The seismic anisotropy of ­MgCO3-C2/m
and ­Mg2CO4-P21/c showed obvious nonlinear dependence on pressure. This is mainly due to the nonlinear
pressure of wave velocity caused by the nonlinear pressure dependence of the elastic moduli of M ­ gCO3-C2/m
and ­Mg2CO4-P21/c, especially their shear moduli.
Although the previous e­ xperimental4–6 and t­ heoretical7–13 studies obtained M
­ gCO3-C2/m at high tempera-
ture and pressure, they did not consider the reaction with MgO, the main mineral of the Earth’s lower mantle.
The ­theoretical14 and e­ xperimental15 results of Gavryushkin et al. show that M­ gCO3 reacts with MgO to form
­Mg2CO4-P21/c orthocarbonate under the temperature and pressure conditions of the lower mantle. By compar-
ing the high-pressure physical properties of M ­ gCO3-C2/m and M ­ g2CO4-P21/c, it is found that their seismic
anisotropy is quite different, while the equation of state, elastic modulus, density and wave velocity have similar
relationship with pressure. The low wave velocities of ­Mg2CO4-P21/c are more suitable to explain the existence

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Figure 10.  3D representation of the VP and VS and the shear wave splitting and polarization vectors of
­ g2CO4-P21/c at various pressures.
M

16 40.0

15 37.5

Seismic anisotropy AS (%)

Seismic anisotropy AP (%)

14 Mg2CO4-P21/c 35.0
MgCO3-C2/m
MgCO3-C2/m, Li and Stackhouse, 2020
13 32.5
Mg2CO4-P21/c
MgCO3-C2/m
MgCO3-C2/m, Li and Stackhouse, 2020
12 30.0

11 27.5

10 25.0
60 80 100 120 140 60 80 100 120 140

Pressure (GPa) Pressure (GPa)

Figure 11.  Seismic anisotropy of M

­ gCO3-C2/m and ­Mg2CO4-P21/c.

of low-velocity zone near the subducting slab. Therefore, we believe that M

­ g2CO4-P21/c may exist in the deep
mantle, providing strong evidence for carbon storage in carbonate minerals, which may be the main reason why
carbonate rocks cannot be detected in the lower mantle.

Minimum thermal conductivity. The thermal conductivity of minerals is critical to understanding the
Earth’s thermal balance and h ­ istory43. The minimum thermal conductivity of M ­ g2CO4-P21/c
­ gCO3-C2/m and M
are calculated using Cahill’s model:

Kmin = (kB 2.48)n2/3 (vP + 2vS ) (5)



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Kmin a Kmin b
5.0 [100] direcon 5.0 [100] direcon

Minimum thermal conductivity (W/mK)

[010] direcon [010] direcon
[001] direcon [001] direcon

4.5 4.5

4.0 4.0

3.5 3.5

3.0 3.0
60 80 100 120 140 60 80 100 120 140

Pressure (GPa) Pressure (GPa)

Figure 12.  Minimum thermal conductivity of ­MgCO3-C2/m (a) and ­Mg2CO4-P21/c (b).

The anisotropy of the minimum thermal conductivity can be calculated by changing Eq. (5) into the follow-
ing form:

Kmin = (kB 2.48)n2/3 (vP + vS1 + vS2 ) (6)



where kB is Boltzmann’s constant, n is the atomic number density per unit volume. The minimum thermal
conductivities of ­MgCO3-C2/m and ­Mg2CO4-P21/c are shown in Fig. 12, and it is found that their minimum
thermal conductivities increase with the increase of pressure, and that of M ­ gCO3-C2/m is larger than that of
­Mg2CO4-P21/c. In the studied pressure range, Kmin[010] > Kmin[100] > Kmin[001], indicating that the thermal con-
ductivity in the [010] direction is the largest and the thermal conductivity in the [001] direction is the smallest.

Thermodynamic properties. Thermodynamic parameters are the preconditions for deriving the thermal
state of the Earth’s interior. Therefore, the thermodynamic properties of M­ gCO3-C2/m and M ­ g2CO4-P21/c are
crucial for studying the thermal state of the lower mantle. The constant volume heat capacity (CV) and the ther-
mal expansion coefficient (α) of ­MgCO3-C2/m and M ­ g2CO4-P21/c at various pressures are depicted in Figs. 13
and 14, respectively. The CV and α of M­ gCO3-C2/m are larger than those of M­ g2CO4-P21/c under the same pres-
sure.

Conclusions
On the basis of verifying the structure and equation of state of M
­ gCO3-C2/m, the phase transition pressure of
­Mg2CO4-P21/c is determined. The high-pressure physical properties of ­MgCO3-C2/m and M ­ g2CO4-P21/c at
50–140 GPa are investigated by first-principles calculations. By comparison, it is found that the elastic modu-
lus and wave velocity of ­Mg2CO4-P21/c are smaller than those of ­MgCO3-C2/m, and the density and seismic
anisotropy are larger than those of M ­ gCO3-C2/m. The low wave velocity of M ­ g2CO4-P21/c may be more suit-
able to explain the existence of the low-velocity zone near the subducting slab. Therefore, it is believed that
­Mg2CO4-P21/c may exist in the deep mantle, providing strong evidence for carbon storage in carbonates and the
reason why it cannot be detected in the lower mantle. The minimum thermal conductivity of ­MgCO3-C2/m is
greater than that of ­Mg2CO4-P21/c, and their minimum thermal conductivity is the largest in the [010] direction
and the smallest in the [001] direction. The constant volume heat capacity CV and thermal expansion coefficient
α of ­MgCO3-C2/m are larger than those of ­Mg2CO4-P21/c. Unfortunately, there are no experimental data on
the elastic constants, thermodynamic parameters, and minimum thermal conductivity of ­MgCO3-C2/m and
­Mg2CO4-P21/c, so further verification is required.

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800 200
a b

Constant volume heat capacity CV (J/mol K)

600 150

400 100

60 GPa 60 GPa
90 GPa 90 GPa
200 120 GPa 50 120 GPa

0 0
0 500 1000 1500 2000 0 500 1000 1500 2000

Temperature (K) Temperature (K)

Figure 13.  Constant volume heat capacity CV of ­MgCO3-C2/m (a) and ­Mg2CO4-P21/c (b).

5 0.8
60 GPa a 60 GPa b
90 GPa 90 GPa
Thermal expansion coefcients (10-5/K)

4 120 GPa 120 GPa

0.6

0.4

0.2
1

0 0.0
0 500 1000 1500 2000 0 500 1000 1500 2000

Temperature (K) Temperature (K)

Figure 14.  Thermal expansion coefficient α of ­MgCO3-C2/m (a) and ­Mg2CO4-P21/c (b).

Data availability
The datasets used and/or analysed during the current study available from the corresponding author on reason-
able request.

Received: 11 October 2022; Accepted: 9 November 2022

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Acknowledgements
This work is supported by the Industrial Support and Guidance Project of Colleges and Universities of Gansu
Province (No. 2022CYZC-37), the Key Natural Science Foundation of Gansu Province (No. 20JR5RA211) and
the Talent Innovation and Entrepreneurship Project of Lanzhou City (No. 2020-RC-18).

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Author contributions
Z.-J.L. designed the calculations and wrote the manuscript. X.-W.S. and C.-R.Z. analyzed the results. J.-Q.J. and
T.L. performed partial calculations. All authors reviewed the manuscript.

Competing interests
The authors declare no competing interests.

Additional information
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