Heat capacity and thermal expansion of metal crystalline materials based on dynamic thermal vibration

TL;DR

This paper introduces a dynamic thermal vibration method to accurately calculate heat capacity and thermal expansion of metals from 0K to melting point, aligning well with experimental data.

Contribution

It presents a novel approach that accounts for temperature-dependent vibrational frequencies and structural deformation in metals, improving thermodynamic property predictions.

Findings

Accurately predicts heat capacity and TEC for various metals.

Results agree well with experimental data across temperature range.

Provides an efficient method for thermodynamic calculations of metals.

Abstract

A novel approach based on dynamic thermal vibration is proposed to calculate the heat capacity and thermal expansion coefficient (TEC) for metal crystalline materials from 0K to the melting point. The motion of metal atomic clusters is decomposed into structural deformation and thermal vibration. Then thermal vibration equations are established by the fourth-order Taylor expansion of Hamiltonian at the transient structural deformation position $\bar{\mathbf{x}}$. As a result, the thermal vibration frequencies dynamically change with the structural deformation positions and temperatures. A parameter $\bar\delta (\bar{\mathbf{x}}, T)$ is newly introduced to illustrate how the thermal vibration frequencies vary with the temperature $T$. Besides, the modified temperature-dependent Gr\"uneisen parameter $\bar \gamma (\bar{\mathbf{x}}, T)$ is given. Finally, the formulae of heat capacity and TEC for metal crystalline materials are derived from the dynamic thermal vibration frequencies and $\bar \delta (\bar{\mathbf{x}}, T)$ as well as $\bar \gamma (\bar{\mathbf{x}}, T)$. The numerical results of heat capacity and TEC for metals Cu, Al, Au, Ag, Ni, Pd, Pt and Pb show a temperature dependence and agree well with the experimental data from 0K to the melting point. This work suggests an efficient approach to calculate thermodynamic properties of metal materials for a wide range of temperatures, up to the melting point.