van der Waals forces stabilize low-energy polymorphism in B2O3: Implications for the crystallization anomaly

Guillaume Ferlat (1) , Maria Hellgren (1) , François-Xavier Coudert (2) , Henri Hay (1) , Francesco Mauri (3, 1) , Michele Casula (1)

1 IMPMC - Institut de minéralogie, de physique des matériaux et de cosmochimie
2 IRCP - Institut de Recherche de Chimie Paris
3 Dipartimento di Fisica [Roma La Sapienza]

The cohesive energies and structural properties of recently predicted, and never synthesized, B2O3 polymorphs are investigated from first principles using density functional theory and high-accuracy many-body methods, namely, the random phase approximation and quantum Monte Carlo. We demonstrate that the van der Waals forces play a key role in making the experimentally known polymorph (B2O3-I) the lowest in energy, with many competing metastable structures lying only a few kcal/mol above. Remarkably, all metastable crystals are comparable in energy and density to the glass, while having anisotropic and mechanically soft structures. Furthermore, the best metastable polymorph according to our stability criteria has a structural motif found in both the glass and a recently synthesized borosulfate compound. Our findings provide a framework for understanding the B2O3 anomalous behavior, namely, its propensity to vitrify in a glassy structure drastically different from the known crystal.

Domaines: Chimie théorique et/ou physique; Matériaux

Guillaume Ferlat, Maria Hellgren, François-Xavier Coudert, Henri Hay, Francesco Mauri, et al.. van der Waals forces stabilize low-energy polymorphism in B2O3: Implications for the crystallization anomaly. Physical Review Materials, 2019, 3 (6), pp.063603. ⟨10.1103/PhysRevMaterials.3.063603⟩. ⟨hal-02152193⟩