Microscopic view of heat capacity of matter: solid, liquid, and gas

TL;DR

This paper presents a microscopic analysis of heat capacity across solid, liquid, and gas phases, revealing a unified framework based on atomic-level dynamics that overcomes previous theoretical limitations.

Contribution

It introduces a microscopic approach using normal modes and molecular dynamics to unify the description of heat capacity in all phases of matter.

Findings

Heat capacity of liquids can be modeled by combining solid-like and gas-like degrees of freedom.

The framework applies across a wide range of temperatures and pressures.

Results challenge traditional separate phase descriptions of heat capacity.

Abstract

Understanding thermodynamics in liquids at the atomic level is challenging because of strong atomic interactions and lack of symmetry. Recent prior theoretical works have focused on describing heat capacity of liquids in terms of phonon-like excitations but often rely on fitting parameters and ad hoc assumptions. In this work, we perform microscopic analysis on instantaneous normal modes and velocity autocorrelations on molecular dynamics simulations of single element systems over wide ranges of temperature (up to $10^8$ K) and pressure (up to 1 TPa). Our results demonstrate that heat capacity of liquids can be described by a combination of both solid-like and gas-like degrees of freedom, leading to a unified framework to describe heat capacity of all three phases of matter: solid, liquid, and gas.