First-Principles Study of the Effects of Phase Transitions and Decomposition on the Lattice Thermal Conductivity of Calcite
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摘要: 矿物的晶格热导率对地球内部的热流和温度分布具有重要影响。方解石的主要成分为碳酸钙（CaCO3），其可以随俯冲进入地球深部，是地球深部重要的碳来源。随着地球深度的变化，CaCO3发生相变和热分解，其物理性质也会受到影响。采用第一性原理结合晶格动力学方法研究了方解石相变及热分解前后的热导率变化。计算结果表明：发生方解石Ⅰ至方解石Ⅱ相变时，热导率减小，而在更高压力下发生相变时，热导率均有不同程度的增大；文石及后文石的热导率随压力的升高接近线性增加，其中后文石随压力变化更为明显；热分解产物CaO的热导率明显高于方解石的热导率，会加速局部区域的热传导。对相关热力学参数进行分析，发现声子群速度与非谐散射率共同决定了相变和分解导致的热导率变化。Abstract: The lattice thermal conductivity of minerals plays a critical role in controlling heat flow and temperature distribution in the Earth’s interior. Calcite, primarily composed of calcium carbonate (CaCO3), can be subducted into the deep Earth and serves as an important carbon source. As pressure and temperature conditions change with depth, CaCO3 undergoes phase transitions and thermal decomposition, which significantly affect its physical properties. In this study, we investigate the effects on thermal conductivity of calcite induced phase transitions and thermal decomposition using first-principles calculations combined with lattice dynamics. Our results show that the calcite Ⅰ → calcite Ⅱ phase transition leads to a reduction in thermal conductivity, whereas subsequent phase transitions at higher pressures result in increase. The thermal conductivity of aragonite and post-aragonite increases nearly linearly with pressure increasing, and the latter exhibiting a stronger pressure dependence. Upon thermal decomposition, the CaO exhibits significantly higher thermal conductivity than that of calcite, which may enhance local heat transfer. Analysis of relevant thermodynamic parameters indicates that the changes in thermal conductivity induced by phase transitions and decomposition are collectively determined by phonon group velocity and anharmonic scattering rates.
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Key words:
- lattice thermal conductivity /
- calcite /
- phase transition /
- first-principles /
- high pressure /
- aragonite
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图 1 CaO和CaCO3的各个相在各自压力边界下的声子谱
Figure 1. Phonon spectra for phases of CaO and CaCO3 at their respective pressure boundaries
图 3 300 K条件下方解石及相变产物随压力变化的热导率
Figure 3. Thermal conductivity of the phases of calcite at 300 K
图 4 方解石Ⅰ、Ⅱ和CaO在1.5 GPa下的热导率
Figure 4. Thermal conductivity of calcite Ⅰ, calcite Ⅱ, and CaO at 1.5 GPa
图 5 CaCO3的各个相在各自压力边界下的热导率
Figure 5. Thermal conductivity of each phase of CaCO3 under their respective pressure boundaries
图 6 1.5 GPa下方解石Ⅰ、方解石Ⅱ和CaO的累积热导率
Figure 6. Cumulative thermal conductivity of calcite Ⅰ, calcite Ⅱ, and CaO at 1.5 GPa
图 7 方解石Ⅰ、Ⅱ在1.5 GPa下的(a) 非谐散射率、(b) 声子群速度与(c) 加权相空间
Figure 7. (a) Anharmonic scattering rate, (b) phonon group velocity, and (c) weighted phase space of calcite Ⅰ and Ⅱ at 1.5 GPa
图 8 方解石Ⅰ、CaO在1.5 GPa下的(a) 非谐散射率、(b) 声子群速度和(c) 加权相空间
Figure 8. (a) Anharmonic scattering rate, (b) phonon group velocity, and (c) weighted phase space of calcite Ⅰ and CaO at 1.5 GPa
表 1 CaCO3各相及CaO的相关计算参数
Table 1. Calculation parameters for CaCO3 and CaO
Structure Space group K-point Q-point Supercell Calcite Ⅰ R3c 3×3×1 13×13×7 2×2×1 Calcite Ⅱ P21c 2×2×2 11×13×7 2×2×2 Aragonite Pnma 4×2×3 13×11×13 2×2×2 Post-aragonite Pmnm 2×2×2 16×16×16 2×2×2 CaO $Fm{\overline3}m $ 2×2×2 16×16×16 2×2×2 
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[1] BRENKER F E, VOLLMER C, VINCZE L, et al. Carbonates from the lower part of transition zone or even the lower mantle [J]. Earth and Planetary Science Letters, 2007, 260(1/2): 1–9. doi: 10.1016/j.epsl.2007.02.038 [2] HUANG S C, FARKAŠ J, JACOBSEN S B. Stable calcium isotopic compositions of Hawaiian shield lavas: evidence for recycling of ancient marine carbonates into the mantle [J]. Geochimica et Cosmochimica Acta, 2011, 75(17): 4987–4997. doi: 10.1016/j.gca.2011.06.010 [3] JOHNSTON F K B, TURCHYN A V, EDMONDS M. Decarbonation efficiency in subduction zones: implications for warm Cretaceous climates [J]. Earth and Planetary Science Letters, 2011, 303(1/2): 143–152. doi: 10.1016/j.epsl.2010.12.049 [4] KAMINSKY F. Mineralogy of the lower mantle: a review of ‘super-deep’ mineral inclusions in diamond [J]. Earth-Science Reviews, 2012, 110(1/2/3/4): 127–147. doi: 10.1016/j.earscirev.2011.10.005 [5] KAMINSKY F V, WIRTH R, SCHREIBER A. Carbonatitic inclusions in deep mantle diamond from Juina, Brazil: new minerals in the carbonate-halide association [J]. The Canadian Mineralogist, 2013, 51(5): 669–688. doi: 10.3749/canmin.51.5.669 [6] KERRICK D M, CONNOLLY J A D. Metamorphic devolatilization of subducted oceanic metabasalts: implications for seismicity, arc magmatism and volatile recycling [J]. Earth and Planetary Science Letters, 2001, 189(1/2): 19–29. doi: 10.1016/s0012-821x(01)00347-8 [7] THOMSON A R, WALTER M J, KOHN S C, et al. Slab melting as a barrier to deep carbon subduction [J]. Nature, 2016, 529(7584): 76–79. doi: 10.1038/nature16174 [8] GAVRYUSHKIN P N, MARTIROSYAN N S, INERBAEV T M, et al. Aragonite-Ⅱ and CaCO3-Ⅶ: new high-pressure, high-temperature polymorphs of CaCO3 [J]. Crystal Growth & Design, 2017, 17(12): 6291–6296. doi: 10.1021/acs.cgd.7b00977 [9] LI X Y, ZHANG Z G, LIN J F, et al. New high-pressure phase of CaCO3 at the topmost lower mantle: implication for the deep-mantle carbon transportation [J]. Geophysical Research Letters, 2018, 45(3): 1355–1360. doi: 10.1002/2017GL076536 [10] LITASOV K D, SHATSKIY A, GAVRYUSHKIN P N, et al. p-V-T equation of state of CaCO3 aragonite to 29 GPa and 1 673 K: in situ X-ray diffraction study [J]. Physics of the Earth and Planetary Interiors, 2017, 265: 82–91. doi: 10.1016/j.pepi.2017.02.006 [11] LOBANOV S S, DONG X, MARTIROSYAN N S, et al. Raman spectroscopy and X-ray diffraction of sp3 CaCO3 at lower mantle pressures [J]. Physical Review B, 2017, 96(10): 104101. doi: 10.1103/PhysRevB.96.104101 [12] OGANOV A R, ONO S, MA Y M, et al. Novel high-pressure structures of MgCO3, CaCO3 and CO2 and their role in Earth’s lower mantle [J]. Earth and Planetary Science Letters, 2008, 273(1/2): 38–47. doi: 10.1016/j.epsl.2008.06.005 [13] PICKARD C J, NEEDS R J. Structures and stability of calcium and magnesium carbonates at mantle pressures [J]. Physical Review B, 2015, 91(10): 104101. doi: 10.1103/PhysRevB.91.104101 [14] SANTOS S S M, MARCONDES M L, JUSTO J F, et al. Stability of calcium and magnesium carbonates at Earth’s lower mantle thermodynamic conditions [J]. Earth and Planetary Science Letters, 2019, 506: 1–7. doi: 10.1016/j.epsl.2018.10.030 [15] SMITH D, LAWLER K V, MARTINEZ-CANALES M, et al. Postaragonite phases of CaCO3 at lower mantle pressures [J]. Physical Review Materials, 2018, 2(1): 013605. doi: 10.1103/physrevmaterials.2.013605 [16] CATALLI K, WILLIAMS Q. Letter: a high-pressure phase transition of calcite-Ⅲ [J]. American Mineralogist, 2005, 90(10): 1679–1682. doi: 10.2138/am.2005.1954 [17] IVANOV B A, DEUTSCH A. The phase diagram of CaCO3 in relation to shock compression and decomposition [J]. Physics of the Earth and Planetary Interiors, 2002, 129(1/2): 131–143. doi: 10.1016/S0031-9201(01)00268-0 [18] SALJE E, VISWANATHAN K. The phase diagram calcite-aragonite as derived from the crystallographic properties [J]. Contributions to Mineralogy and Petrology, 1976, 55(1): 55–67. doi: 10.1007/BF00372754 [19] WOLF G, GüNTHER C. Thermophysical investigations of the polymorphous phases of calcium carbonate [J]. Journal of Thermal Analysis and Calorimetry, 2001, 65(3): 687–698. doi: 10.1023/A:1011991124181 [20] CARRASCO-BUSTURIA D. The temperature-pressure phase diagram of the calcite Ⅰ–calcite Ⅱ phase transition: a first-principles investigation [J]. Journal of Physics and Chemistry of Solids, 2021, 154: 110045. doi: 10.1016/j.jpcs.2021.110045 [21] SUITO K, NAMBA J, HORIKAWA T, et al. Phase relations of CaCO3 at high pressure and high temperature [J]. American Mineralogist, 2001, 86(9): 997–1002. doi: 10.2138/am-2001-8-906 [22] JAMIESON J C. Phase equilibrium in the system calcite-aragonite [J]. The Journal of Chemical Physics, 1953, 21(8): 1385–1390. doi: 10.1063/1.1699228 [23] LAMBERT I B, WYLLIE P J. Melting in the deep crust and upper mantle and the nature of the low velocity layer [J]. Physics of the Earth and Planetary Interiors, 1970, 3: 316–322. doi: 10.1016/0031-9201(70)90068-3 [24] MERLINI M, HANFLAND M, CRICHTON W A. CaCO3-Ⅲ and CaCO3-Ⅵ, high-pressure polymorphs of calcite: possible host structures for carbon in the Earth’s mantle [J]. Earth and Planetary Science Letters, 2012, 333/334: 265–271. [25] ONO S, KIKEGAWA T, OHISHI Y, et al. Post-aragonite phase transformation in CaCO3 at 40 GPa [J]. American Mineralogist, 2005, 90(4): 667–671. doi: 10.2138/am.2005.1610 [26] PALAICH S E M, HEFFERN R A, HANFLAND M, et al. High-pressure compressibility and thermal expansion of aragonite [J]. American Mineralogist, 2016, 101(7): 1651–1658. doi: 10.2138/am-2016-5528 [27] SANTILLÁN J, WILLIAMS Q. A high pressure X-ray diffraction study of aragonite and the post-aragonite phase transition in CaCO3 [J]. American Mineralogist, 2004, 89(8/9): 1348–1352. doi: 10.2138/am-2004-8-925 [28] OGANOV A R, GLASS C W, ONO S. High-pressure phases of CaCO3: crystal structure prediction and experiment [J]. Earth and Planetary Science Letters, 2006, 241(1/2): 95–103. doi: 10.1016/j.epsl.2005.10.014 [29] ARAPAN S, AHUJA R. High-pressure phase transformations in carbonates [J]. Physical Review B, 2010, 82(18): 184115. doi: 10.1103/PhysRevB.82.184115 [30] YAO X, XIE C W, DONG X, et al. Novel high-pressure calcium carbonates [J]. Physical Review B, 2018, 98(1): 014108. doi: 10.1103/physrevb.98.014108 [31] DEKURA H, TSUCHIYA T. Ab initio lattice thermal conductivity of MgO from a complete solution of the linearized Boltzmann transport equation [J]. Physical Review B, 2017, 95(18): 184303. doi: 10.1103/physrevb.95.184303 [32] HUANG D, LIU H, HOU M Q, et al. Elastic properties of CaCO3 high pressure phases from first principles [J]. Chinese Physics B, 2017, 26(8): 089101. doi: 10.1088/1674-1056/26/8/089101 [33] JIANG C L, ZENG W, LIU F S, et al. First-principles analysis of vibrational modes of calcite, magnesite and dolomite [J]. Journal of Physics and Chemistry of Solids, 2019, 131: 1–9. doi: 10.1016/j.jpcs.2019.03.011 [34] MARCONDES M L, WENTZCOVITCH R M, ASSALI L V C. Importance of van der Waals interaction on structural, vibrational, and thermodynamic properties of NaCl [J]. Solid State Communications, 2018, 273: 11–16. doi: 10.1016/j.ssc.2018.01.008 [35] QIN T, WENTZCOVITCH R M, UMEMOTO K, et al. Ab initio study of water speciation in forsterite: importance of the entropic effect [J]. American Mineralogist, 2018, 103(5): 692–699. doi: 10.2138/am-2018-6262 [36] ROBERTSON E C. Thermal properties of rocks [R]. 1988. [37] MA Y Y, YANG S, HE K H, et al. First principles study of the lattice thermal conductivity of alkaline earth oxides [J]. Computational Materials Science, 2022, 210: 111446. doi: 10.1016/j.commatsci.2022.111446 [38] VYAS P, PATEL A B, BHATT N K. Thermal conductivity of CaO under the conditions of the Earth’s interior [J]. Physical Review B, 2024, 109(1): 014302. doi: 10.1103/physrevb.109.014302 [39] DEKURA H, TSUCHIYA T. Lattice thermal conductivity of MgSiO3 postperovskite under the lowermost mantle conditions from ab initio anharmonic lattice dynamics [J]. Geophysical Research Letters, 2019, 46(22): 12919–12926. doi: 10.1029/2019GL085273 [40] OUYANG Y L, YU C Q, HE J, et al. Accurate description of high-order phonon anharmonicity and lattice thermal conductivity from molecular dynamics simulations with machine learning potential [J]. Physical Review B, 2022, 105(11): 115202. doi: 10.1103/PhysRevB.105.115202 [41] WANG D, WU Z Q, DENG X. Thermal conductivity of Fe-bearing bridgmanite and post-perovskite: implications for the heat flux from the core [J]. Earth and Planetary Science Letters, 2023, 621: 118368. doi: 10.1016/j.epsl.2023.118368 [42] KRESSE G, FURTHMÜLLER J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set [J]. Physical Review B, 1996, 54(16): 11169–11186. doi: 10.1103/PhysRevB.54.11169 [43] KRESSE G, JOUBERT D. From ultrasoft pseudopotentials to the projector augmented-wave method [J]. Physical Review B, 1999, 59(3): 1758–1775. doi: 10.1103/PhysRevB.59.1758 [44] BLÖCHL P E. Projector augmented-wave method [J]. Physical Review B, 1994, 50(24): 17953–17979. doi: 10.1103/PhysRevB.50.17953 [45] HOHENBERG P, KOHN W. Inhomogeneous electron gas [J]. Physical Review, 1964, 136(3B): B864–B871. doi: 10.1103/PhysRev.136.B864 [46] KOHN W, SHAM L J. Self-consistent equations including exchange and correlation effects [J]. Physical Review, 1965, 140(4A): A1133–A1138. doi: 10.1103/PhysRev.140.A1133 [47] MONKHORST H J, PACK J D. Special points for Brillouin-zone integrations [J]. Physical Review B, 1976, 13(12): 5188–5192. doi: 10.1103/PhysRevB.13.5188 [48] TOGO A, CHAPUT L, TANAKA I. Distributions of phonon lifetimes in Brillouin zones [J]. Physical Review B, 2015, 91(9): 094306. doi: 10.1103/PhysRevB.91.094306 [49] LIANG T, CHEN W Q, HU C E, et al. Lattice dynamics and thermal conductivity of lithium fluoride via first-principles calculations [J]. Solid State Communications, 2018, 272: 28–32. doi: 10.1016/j.ssc.2018.01.004 [50] HAIGIS V, SALANNE M, JAHN S. Thermal conductivity of MgO, MgSiO3 perovskite and post-perovskite in the Earth’s deep mantle [J]. Earth and Planetary Science Letters, 2012, 355/356: 102–108. doi: 10.1016/j.epsl.2012.09.002 [51] IMADA S, OHTA K, YAGI T, et al. Measurements of lattice thermal conductivity of MgO to core-mantle boundary pressures [J]. Geophysical Research Letters, 2014, 41(13): 4542–4547. doi: 10.1002/2014GL060423 [52] OHTA K, YAGI T, HIROSE K, et al. Thermal conductivity of ferropericlase in the Earth’s lower mantle [J]. Earth and Planetary Science Letters, 2017, 465: 29–37. doi: 10.1016/j.epsl.2017.02.030 [53] LI W, MINGO N. Lattice dynamics and thermal conductivity of skutterudites CoSb3 and IrSb3 from first principles: why IrSb3 is a better thermal conductor than CoSb3 [J]. Physical Review B, 2014, 90(9): 094302. doi: 10.1103/PhysRevB.90.094302 -
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