Nonlinear dynamic elastic moduli from equilibrium stress fluctuations

TL;DR

This paper derives fluctuation formulas for nonlinear dynamic elastic moduli from equilibrium stress fluctuations, enabling computation of anharmonic viscoelastic response without explicit deformation.

Contribution

It introduces the first fluctuation formulas for nonlinear time-dependent moduli based on equilibrium molecular dynamics simulations.

Findings

Derived transient-time correlation function expressions for nonlinear moduli

Formulas recover known quasi-static and linear results in limits

Enables calculation of anharmonic viscoelastic response from equilibrium data

Abstract

Fluctuation formulas for elastic and viscoelastic moduli allow their computation from equilibrium molecular dynamics simulations, avoiding explicit nonequilibrium deformation protocols. While such expressions are well established for the quasi-static moduli, and also the linear dynamic moduli, no fluctuation formula exists for the nonlinear time-dependent moduli that govern anharmonic viscoelastic response under finite time-dependent strains. In this work we derive transient-time correlation function expressions for both the linear and the nonlinear dynamic moduli, starting from the DOLLS/SLLOD equations of motion for irrotational motion. The resulting formulas involve equilibrium time correlations of the stress tensor and Born-kinetic terms, and they recover the known quasi-static and linear dynamic results in the appropriate limits.