Phonon dispersion in two-dimensional solids from atomic probability distributions

TL;DR

This paper introduces a harmonic linear response method to compute phonon dispersion in 2D materials from equilibrium simulations, effectively capturing anharmonic effects at finite temperatures.

Contribution

A novel harmonic linear response approach based on equilibrium path integral simulations for calculating phonon dispersions in 2D materials.

Findings

Validated on graphene monolayer, bilayer, and graphane.

Captured temperature-dependent anharmonic effects.

Demonstrated method's effectiveness in finite-temperature phonon calculations.

Abstract

We propose a harmonic linear response (HLR) method to calculate the phonon dispersion relations of two-dimensional (2D) layers from equilibrium simulations at finite temperature. This HLR approach is based on the linear response of the system, as derived from the analysis of its centroid density in equilibrium path integral simulations. In the classical limit, this approach is closely related to those methods that study vibrational properties by the diagonalization of the covariance matrix of atomic fluctuations. The validity of the method is tested in the calculation of the phonon dispersion relations of a graphene monolayer, a graphene bilayer, and graphane. Anharmonic effects in the phonon dispersion relations of graphene are demonstrated by the calculation of the temperature dependence of the following observables: the kinetic energy of the carbon atoms, the vibrational frequency of the optical $E_{2g}$ mode, and the elastic moduli of the layer.