Melting properties of a simple tight-binding model of transition metals: I.The region of half-filled d-band

TL;DR

This paper models the melting properties of transition metals using a simple tight-binding approach, focusing on the d-band filling near half, and compares results with first-principles data for molybdenum.

Contribution

It introduces a minimal tight-binding model that accurately predicts melting behavior of transition metals near half-filled d-bands, calibrated to molybdenum data.

Findings

Model reproduces phonon dispersion of Mo

Accurately predicts melting properties close to first-principles results

Provides insight into the relation between bonding energy and melting behavior

Abstract

We present calculations of the free energy, and hence the melting properties, of a simple tight-binding model for transition metals in the region of d-band filling near the middle of a d-series, the parameters of the model being designed to mimic molybdenum. The melting properties are calculated for pressures ranging from ambient to several Mbar. The model is intended to be the simplest possible tight-binding representation of the two basic parts of the energy: first, the pairwise repulsion due to Fermi exclusion; and second, the d-band bonding energy described in terms of an electronic density of states that depends on structure. In addition to the number of d-electrons, the model contains four parameters, which are adjusted to fit the pressure dependent d-band width and the zero-temperature pressure-volume relation of Mo. We show that the resulting model reproduces well the phonon dispersion relations of Mo in the body-centred-cubic structure, as well as the radial distribution function of the high-temperature solid and liquid given by earlier first-principles simulations. Our free-energy calculations start from the free energy of the liquid and solid phases of the purely repulsive pair-potential model, without d-band bonding. The free energy of the full tight-binding model is obtained from this by thermodynamic integration. The resulting melting properties of the model are quite close to those given by earlier first-principles work on Mo. An interpretation of these melting properties is provided by showing how they are related to those of the purely repulsive model.