Internal degrees of freedom and transport of benzene on graphite

TL;DR

This study analyzes how the chaotic internal degrees of freedom of benzene molecules on graphite influence their diffusion and drift, combining analytical methods with molecular-dynamics simulations to predict and compare friction and diffusion behaviors.

Contribution

It provides a novel analytical framework linking internal molecular chaos with surface diffusion, validated by molecular-dynamics simulations and experimental comparisons.

Findings

Thermal noise minimally affects internal chaos but influences friction and diffusion.

Torsion in benzene significantly impacts surface friction.

Theoretical predictions align well with neutron spin echo experimental data.

Abstract

In this paper, the chaotic internal degrees of freedom of a benzene molecule adsorbed on a graphite substrate, their interplay with thermal noise, and their effects on the diffusion and drift are investigated analytically by making use of the presence of two different time scales as well as by molecular-dynamics simulations. The effects of thermal noise are investigated, and it is found that noise does not significantly alter the dynamics of the internal degrees of freedom, yet affects the friction and diffusion of the center of mass. Qualitative and quantitative theoretical predictions for the friction and diffusion of the molecule on the substrate are made and are compared to molecular-dynamics simulations. Contributions to the friction and diffusion from the finite heat bath as well as the slow dynamics of the center of mass are formally identified. It is shown that the torsion in benzene, which dominates the nonlinear coupling, significantly affects the friction of the molecule on the surface. The results compare favorably with recent results from He/neutron spin echo experiments on this system. Based on the analytical and numerical results, some suggestions are made for experimental conditions under which the effects of internal degrees of freedom might be observable.