(10.4) Face of Ordered and Disordered Dolomite, MgCa(CO3)2: A Computational Study to Reveal the Growth Mechanism
Abstract
:1. Introduction
2. Computational Details
3. Results and Discussion
3.1. Bulk Structures of Dolomite
3.2. Surface Terminations and Surface Energies of the (10.4) Faces of Dolomite
- The surface energy of the (10.4) face of calcite (0.507 J/m2) is slightly higher than that of magnesite (0.493 J/m2). Previous surface energy calculations on the (10.4) face of calcite and magnesite were performed by our research group, always using the B3LYP Hamiltonian but considering a poorer basis sets: 0.508 and 0.501 J/m2 for calcite and magnesite, respectively [39]. These small variations in the surface energy values suggest that our estimates are barely affected by the Basis Set Superposition Error (BSSE) [23]. Indeed, if the use of richer basis sets does not produce significant variations in the surface energy value, then it is licit to suppose that our estimates are reliable.
- The surface energies of the , and faces are lower than those of calcite and magnesite: 0.489, 0.437 and 0.450 J/m2. This clearly highlights that the (10.4) face is strongly stabilized when there is a mixing of Ca2+ and Mg2+. Furthermore, such stabilization is also a function of the ordering degree of Ca2+ and Mg2+. Indeed, the surface energies of the and faces are decreased by 10.6% and 8.0%, respectively, compared to that of the face. Our calculations suggest that a disordered surface is more stable of an ordered one, in contrast with the findings on the bulk of the crystal [16], where the more stable structure is the ordered one (SC1).
- The two surface terminations obtained by cutting SC4895 have very similar surface energy. This implies an analogous probability to be observed when a crystal grows.
3.3. A Growth Model for Dolomite
4. Conclusions
Author Contributions
Acknowledgments
Conflicts of Interest
References
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This Work | Zucchini et al. [16] | ||||
---|---|---|---|---|---|
Space Group | a (Å) | c (Å) | a (Å) | c (Å) | |
calcite | 5.062 | 17.351 | - | - | |
SC1 | 4.855 | 16.210 | 4.825 | 15.971 | |
SC8 | 4.857 | 16.227 | 4.827 | 16.000 | |
SC4895 | 4.866 | 16.249 | 4.838 | 15.992 | |
magnesite | 4.668 | 15.108 | - | - |
Slab | Space Group | a (Å) | b (Å) | a^b (°) | γ (J/m2) |
---|---|---|---|---|---|
5.0426 | 8.1526 | 90.0 | 0.507 | ||
4.8551 | 7.7862 | 90.0 | 0.489 | ||
9.6602 | 15.4230 | 90.0 | 0.437 | ||
9.6743 | 15.3506 | 89.8 | 0.450 | ||
4.6682 | 7.3769 | 90.0 | 0.493 |
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Bruno, M.; Bittarello, E. (10.4) Face of Ordered and Disordered Dolomite, MgCa(CO3)2: A Computational Study to Reveal the Growth Mechanism. Minerals 2018, 8, 323. https://doi.org/10.3390/min8080323
Bruno M, Bittarello E. (10.4) Face of Ordered and Disordered Dolomite, MgCa(CO3)2: A Computational Study to Reveal the Growth Mechanism. Minerals. 2018; 8(8):323. https://doi.org/10.3390/min8080323
Chicago/Turabian StyleBruno, Marco, and Erica Bittarello. 2018. "(10.4) Face of Ordered and Disordered Dolomite, MgCa(CO3)2: A Computational Study to Reveal the Growth Mechanism" Minerals 8, no. 8: 323. https://doi.org/10.3390/min8080323