Anharmonicity in bcc refractory elements : a detailed ab initio analysis

Abstract

Explicit anharmonicity, defined as the vibrational contribution beyond the quasiharmonic approximation, is qualitatively different between the group V and group VI bcc refractory elements. Group V elements show a small and mostly negative anharmonic entropy, whereas group VI elements have a large positive anharmonic entropy, strongly increasing with temperature. Here, we explain this difference utilizing highly accurate anharmonic free energies and entropies from ab initio calculations for Nb and Ta (group V), and Mo and W (group VI). The numerically calculated entropies are in agreement with prior experimental data. The difference in behavior between the two sets of elements arises not from their high-temperature behavior but rather from the 0K quasiharmonic reference state. We understand this by analyzing the 0K and the high-temperature phonon density of states and the electronic density of states. The qualitative difference disappears when the anharmonicity is instead referenced with a high-temperature effective harmonic potential. However, even for an optimized effective harmonic reference, the remaining effective anharmonicity is significant. The reason is that the anharmonicity in the bcc systems - carried by asymmetric distributions in the nearest neighbors - can never be accounted for by a harmonically restricted potential.