Pauling’s rules guided Monte Carlo search (PAMCARS): A shortcut of predicting inorganic crystal structures

The rapid development of the high-throughput calculations and materials genome approaches in recent years has improved researchers’ ability to design advanced materials. Crystal structure prediction techniques play an important role in high-throughput calculations and materials genome approaches. However, the huge computational cost of the widely used crystal structure prediction techniques based on the global optimization algorithms hinders the researchers from predicting the large or medium-sized crystal structures. In recent years, some metastable materials with excellent electrical, magnetic, optical and catalytic properties have attracted a lot of attention. However, there is currently a lack of a structure prediction technique with high energy resolution near the ground-state structures to meet the growing demands for the prediction of low-energy metastable materials. In this article, a set of easy-operation guidelines for constructing crystal structures is extracted from Pauling’s rules. Based on this set of guidelines, we have designed an algorithm called Pauling’s rules guided Monte Carlo search (PAMCARS), which predict the ground-state and meta-stable inorganic crystal structures of a given composition by combining a classical Monte Carlo search in the configuration space constrained by Pauling’s rules with ab initio structural relaxations. In the actual tests, the crystal structures of carbon allotropes, CaSO4, Ba2TiSi2O8 and BaAlBO3F2 are successfully predicted by this crystal structure prediction algorithm. In addition, a number of unreported high-symmetric metastable crystal structures of carbon, CaSO4 and Ba2TiSi2O8 are also predicted. The successful prediction of graphite layers indicates that PAMCARS is able to predict some layered materials assembled by the Van der Waals forces. Two of the predicted low-energy metastable crystal structures of Ba2TiSi2O8 may explain the property anomaly of Ba2TiSi2O8 around 160 °C. Pauling’s rules guided Monte Carlo search exhibits high efficiency and energy resolution in predicting the ground-state and metastable crystal structures in the tests.