Integration of Quantum, Statistical, and Irreversible Thermodynamics in A Coherent Framework

TL;DR

This paper presents a novel coherent framework integrating quantum, statistical, and irreversible thermodynamics using density functional theory, enabling parameter-free predictions of thermodynamic properties and cross phenomena.

Contribution

It introduces a unified theoretical approach that combines these thermodynamic domains with DFT, allowing accurate, parameter-free predictions of complex thermodynamic behaviors.

Findings

Predicts free energy landscapes with singularities and instabilities.

Accurately predicts coefficients of internal and cross phenomena.

Demonstrates capability of DFT-based inputs without fitting parameters.

Abstract

The combined law of thermodynamics derived by Gibbs laid the foundation of thermodynamics though only applicable to systems without internal processes. Gibbs further derived the classical statistical thermodynamics in terms of the probability of configurations in a system, which was extended to quantum mechanics-based statistical thermodynamics by Landau, while the irreversible thermodynamics was systemized by Onsager and expanded to chemical reactions by Prigogine. The development of density function theory (DFT) by Kohn enabled the quantitative prediction of properties of the ground-state configuration of a system from quantum mechanics. Here, we will present our theories that integrate quantum, statistical, and irreversible thermodynamics in a coherent framework by utilizing the predicative capability of DFT to revise the statistical thermodynamics (zentropy theory) and by keeping the entropy production due to irreversible processes in the combine law of thermodynamics to derive flux equations (theory of cross phenomena). The zentropy theory is shown capable of predicting the free energy landscape including singularity and instability at critical point and emergent positive or negative divergences of properties. The theory of cross phenomena can predict the coefficients of internal processes between conjugate variables (direct phenomena) and non-conjugate variables (cross phenomena) in the combined law of thermodynamics. Both are with inputs from DFT-based calculations only and without fitting parameters.