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Thermodynamics of mixing in the ternary rhombohedral carbonate solid solution, (Ca_(x)Mg_y), Mn_(1-x-y))CO_3, from atomistic simulations

Vinograd, V. L. and Paulsen, N. and Winkler, B. and van de Walle, A. (2010) Thermodynamics of mixing in the ternary rhombohedral carbonate solid solution, (Ca_(x)Mg_y), Mn_(1-x-y))CO_3, from atomistic simulations. CALPHAD - Computer Coupling of Phase Diagrams and Thermochemistry, 34 (1). pp. 113-119. ISSN 0364-5916.

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The effective pairwise interactions in calcitemagnesite, calciterhodochrosite and magnesite rhodochrosite binary systems were evaluated in the diluted limits from the excess enthalpies of supercell structures of the end-members in which pairs of the incoherent (admixed) atoms were inserted at all distinct distances available in a 3×3×1 supercell. The excess enthalpy of mixing within the ternary calcitemagnesiterhodochrosite system was evaluated as a function of the pairwise interactions. Thermal averages of the enthalpy of mixing were calculated with the Monte Carlo method, while the free energies of mixing were obtained by thermodynamic integration. The convex-hull construction was used to visualize miscibility gaps within the ternary. The obtained agreement with the experimentally known phase relations shows that the excess mixing properties within the ternary can be successfully predicted from pairwise interactions calculated in the diluted limits. The method is expected to work only for systems in which many-body interactions can be ignored.

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van de Walle, A.0000-0002-3415-1494
Additional Information:© 2010 Elsevier. Received 12 June 2009; Revised 3 December 2009; accepted 6 January 2010; available online 29 January 2010. VLV acknowledges a research fellowship from the Helmholtz Society (The Virtual Institute for Advanced SolidAqueous Radio-Geochemistry). NP, BW and AvdW acknowledge support from the Deutsche Forschungsgemeinschaft (grant WI 1232/27-1), BMBF (Project 03G0717B) and the US NSF (grant DMR-0907669), respectively. We also wish to thank J.D. Gale and J.A.D. Connolly for the help with calculations.
Funding AgencyGrant Number
Helmholtz Society (The Virtual Institute for Advanced Solid-Aqueous Radio-Geochemistry)UNSPECIFIED
Deutsche ForschungsgemeinschaftWI 1232/27-1
BMBF (Germany)03G0717B
Subject Keywords:Monte Carlo simulations; Solid solutions; Ternary rhombohedral carbonates
Issue or Number:1
Record Number:CaltechAUTHORS:20100520-113007814
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:18362
Deposited By: Jason Perez
Deposited On:21 May 2010 18:29
Last Modified:09 Mar 2020 13:19

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