Quantum-to-classical transition and H-theorem in surface diffusion

Abstract

The so-called quantum-to-classical transition is studied in the surface diffusion dynamics. This continuous and smooth transition is carried out from the Liouville-von Neumann equation by scaling Planck’s constant. As an application, the Brownian motion of an adsorbate on a flat surface is analyzed within the Caldeira–Leggett master equation formalism for the reduced density matrix and the two extreme time behaviors, the ballistic and diffusive motions. In the ballistic time regime, the intermediate scattering function displays a Gaussian function which is governed by the thermal velocity in the classical regime, whereas in the quantum regime, by the initial spreading velocity of the wave packet. Adsorbates behave as a classical or quantum ideal gas. Finally, in the diffusive regime, and starting from the Chudley–Elliott model, the well-known H-function is calculated for three different surface temperatures in the diffusion of H and D on a Pt(111) surface. The main goal of this analysis is whether one can discriminate the irreversibility coming from tunneling or thermal activation diffusion.