V-T Theory of Self Dynamic Response in a Monatomic Liquid

TL;DR

This paper introduces a Vibration-Transit (V-T) theoretical model for self dynamic response in monatomic liquids, accurately matching molecular dynamics results across all wavevectors and capturing both hydrodynamic and free-particle limits.

Contribution

The paper develops a new V-T theory that models vibrational and transit motions in liquids, providing a near a priori, accurate description of self dynamic response across all wavevectors.

Findings

Vibrational contribution matches MD results at all q and t.

Transit motion modeled as a random walk agrees with MD.

Theory correctly approaches free-particle and hydrodynamic limits.

Abstract

A new theoretical model for self dynamic response is developed using Vibration-Transit (V-T) theory, and is applied to liquid sodium at all wavevectors q from the hydrodynamic regime to the free particle limit. In this theory the zeroth-order Hamiltonian describes the vibrational motion in a single random valley harmonically extended to infinity. This Hamiltonian is tractable, is evaluated a priori for monatomic liquids, and the same Hamiltonian (the same set of eigenvalues and eigenvectors) is used for equilibrium and nonequlibrium theory. Here, for the self intermediate scattering function Fself(q,t) we find the vibrational contribution is in near perfect agreement with molecular dynamics (MD) through short and intermediate times, at all q. This is direct confirmation that normal mode vibrational correlations are present in the motion of the liquid state. The primary transit effect is diffusive motion of the vibrational equilibrium positions, as the liquid transits rapidly among random valleys. This motion is modeled as a standard random walk, and the resulting theoretical Fself(q,t) is in excellent agreement with MD results at all q and t. In the limit for q to infinity, the theory automatically exhibits the correct approach to the free-particle limit. Also in the limit for q to zero, the hydrodynamic limit emerges as well. In contrast to the benchmark theories of generalized hydrodynamics and mode coupling, the present theory is near a priori, while achieving modestly better accuracy. Therefore, in our view, it constitutes an improvement over the traditional theories.