Evaluation of the grand-canonical partition function using Expanded Wang-Landau simulations. IV. Performance of many-body force fields and tight-binding schemes for the fluid phases of Silicon

TL;DR

This paper extends the Expanded Wang-Landau simulation method to quantum many-body and classical force field models for silicon, comparing their thermodynamic predictions and effects of nanoconfinement on fluid phases.

Contribution

It introduces a novel application of EWL simulations to tight-binding models and systematically compares classical and quantum models for silicon's fluid phases.

Findings

Quantum models predict a gap in the electronic density of states at high temperatures.

Nanoconfinement significantly reduces liquid densities and alters vapor densities.

Differences in vapor-liquid transition points between models are quantified and compared to experimental data.

Abstract

We extend Expanded Wang-Landau (EWL) simulations beyond classical systems and develop the EWL method for systems modeled with a tight-binding Hamiltonian. We then apply the method to determine the partition function and thus all thermodynamic properties, including the Gibbs free energy and entropy, of the fluid phases of Si. We compare the results from quantum many-body (QMB) tight binding models, which explicitly calculate the overlap between the atomic orbitals of neighboring atoms, to those obtained with classical many-body force fields (CMB), which allow to recover the tetrahedral organization in condensed phases of Si through e.g. a repulsive 3-body term that favors the ideal tetrahedral angle. Along the vapor-liquid coexistence, between 3000K and 6000K, the densities for the two coexisting phases are found to vary significantly (by $5$ orders of magnitude for the vapor and by up to 25% for the liquid) and to provide a stringent test of the models. Transitions from vapor to liquid are predicted to occur for chemical potentials that are $10-15$% higher for CMB models than for QMB models, and a ranking of the force fields is provided by comparing the predictions for the vapor pressure to the experimental data. QMB models also reveal the formation of a gap in the electronic density of states of the coexisting liquid at high temperatures. Subjecting Si to a nanoscopic confinement has a dramatic effect on the phase diagram, with e.g. at 6000K a decrease in liquid densities by about 50% for both CMB and QMB models and an increase in vapor densities between 90% (CMB) and 170% (QMB). The results presented here provide a full picture of the impact of the strategy (CMB or QMB) chosen to model many-body effects on the thermodynamic properties of the fluid phases of Si.