A Model for Transits in Dynamic Response Theory

TL;DR

This paper extends Vibration-Transit (V-T) theory to non-equilibrium properties, specifically modeling the dynamic structure factor S(q,w) in liquids, and demonstrates its effectiveness in fitting molecular dynamics results for liquid sodium.

Contribution

It introduces a parameterized transit model within V-T theory to accurately describe non-equilibrium dynamics in liquids, expanding its applicability beyond thermodynamics.

Findings

The model fits MD results for S(q,w) in liquid sodium.

Transits disrupt vibrational correlations and add inelastic scattering.

Discrepancies at large q are due to multimode vibrational scattering.

Abstract

The first goal of Vibration-Transit (V-T) theory was to construct a tractable approximate Hamiltonian from which the equilibrium thermodynamic properties of monatomic liquids can be calculated. The Hamiltonian for vibrations in an infinitely extended harmonic random valley, together with the universal multiplicity of such valleys, gives an accurate first-principles account of the measured thermodynamic properties of the elemental liquids at melt. In the present paper, V-T theory is extended to non-equilibrium properties, through an application to the dynamic structure factor S(q,w). It was previously shown that the vibrational contribution alone accurately accounts for the Brillouin peak dispersion curve for liquid sodium, as compared both with MD calculations and inelastic x-ray scattering data. Here it is argued that the major effects of transits will be to disrupt correlations within the normal mode vibrational motion, and to provide an additional source of inelastic scattering. We construct a parameterized model for these effects, and show that it is capable of fitting MD results for S(q,w) in liquid sodium. A small discrepancy between model and MD at large q is attributed to multimode vibrational scattering. In comparison, mode coupling theory formulates S(q,w) in terms of processes through which density fluctuations decay. While mode coupling theory is also capable of modeling S(q,w) very well, V-T theory is the more universal since it expresses all statistical averages, thermodynamic functions and time correlation functions alike, in terms of the same motional constituents, vibrations and transits.