Zentropy Theory for Quantitative Prediction of Emergent Behaviors through Symmetry-Breaking Configurations

TL;DR

This paper introduces Zentropy Theory, a novel framework that predicts emergent behaviors in materials by analyzing symmetry-breaking configurations and their statistical competition, extending traditional DFT approaches.

Contribution

The paper develops Zentropy Theory, integrating symmetry-breaking configurations into thermodynamic models to predict emergent properties beyond ground-state configurations.

Findings

Accurate prediction of free energy considering symmetry-breaking states

Emergent behaviors originate from statistical competition among configurations

Phonon properties can be accurately calculated using quasiharmonic approximations

Abstract

Density functional theory (DFT) is the de facto approach for predicting self-consistent-field electronic structures of ground-state configurations of complex atoms, molecules, and solids and providing their property data for materials discovery and design. This capability is greatly enabled by the generalized gradient approximation for exchange-correlation interactions with an important set of exchange-correlation functionals developed by John Perdew and his collaborators in last several decades. The scientific community and the present author's group have greatly benefited from this capability. Over the years, the present author's group has integrated the energetics from DFT-based calculations both at zero K and finite temperature into thermodynamic modeling and developed methods to predict tracer diffusivity, elastic coefficients, interfacial energy, and a number of other properties related to the derivatives of free energy. One key outcome is the accurate prediction of free energy of a system through the consideration of both ground-state and stable symmetry-breaking non-ground-state configurations. It is articulated that phonon properties of all individual configurations can be accurately calculated by quasiharmonic approximations in the temperature and volume ranges of interest, and the emergent behaviors and anharmonicity of a system originate primarily from the statistical competition among all the configurations.