Ab-initio calculations of carbon and boron nitride allotropes and their structural phase transitions using periodic coupled cluster theory

Abstract: We present an ab-initio study of boron nitride as well as carbon allotropes. Their relative thermodynamic stabilities and structural phase transitions from low- to high-density phases are investigated. Pressure-temperature phase diagrams are calculated and compared to experimental findings. The calculations are performed using quantum chemical wavefunction based as well as density functional theories. Our findings reveal that predicted energy differences often depend significantly on the choice of the employed method. Comparison between calculated and experimental results allows for benchmarking the accuracy of various levels of theory. The produced results show that quantum chemical wavefunction based theories allow for achieving systematically improvable estimates. We find that on the level of coupled cluster theories the low- and high-density phases of boron nitride become thermodynamically degenerate at 0 K. This is in agreement with recent experimental findings, indicating that cubic boron nitride is not the thermodynamically stable allotrope at ambient conditions. Furthermore we employ the calculated results to assess transition probabilities from graphitic low-density to diamond-like high-density phases in an approximate manner. We conclude that the stacking order of the parent graphitic material is crucial for the possible formation of meta-stable wurtzite boron nitride and hexagonal carbon diamond also known as lonsdaleite.