# Nuclear quantum effects in graphene bilayers

## TL;DR

This study uses path-integral molecular dynamics to analyze nuclear quantum effects in graphene bilayers, revealing significant quantum contributions to structural properties and vibrational modes across a wide temperature range.

## Contribution

It provides the first detailed quantification of nuclear quantum effects in graphene bilayers, including zero-point expansion and anharmonic vibrational behavior, using advanced simulation techniques.

## Key findings

- Nuclear quantum effects cause a 0.015 Å zero-point expansion in interlayer spacing.
- Out-of-plane compressibility increases with temperature, with a 6% rise at low temperatures due to quantum effects.
- Quantum effects are significant in vibrational modes but diminish with system size.

## Abstract

Graphene bilayers display peculiar electronic and mechanical characteristics associated to their two-dimensional character and relative disposition of the sheets. Here we study nuclear quantum effects in graphene bilayers by using path-integral molecular dynamics simulations, which allow us to consider quantization of vibrational modes and study the effect of anharmonicity on physical variables. Finite-temperature properties are analyzed in the range from 12 to 2000~K. Our results for graphene bilayers are compared with those found for graphene monolayers and graphite. Nuclear quantum effects turn out to be appreciable in the layer area and interlayer distance at finite temperatures. Differences in the behavior of in-plane and real areas of the graphene sheets are discussed. The interlayer spacing has a zero-point expansion of $1.5 \times 10^{-2}$ \AA\ with respect to the classical minimum. The compressibility of graphene bilayers in the out-of-plane direction is found to be similar to that of graphite at low temperature, and increases faster as temperature is raised. The low-temperature compressibility increases by a 6\% due to zero-point motion. Especial emphasis is laid upon atomic vibrations in the out-of-plane direction. Quantum effects are present in these vibrational modes, but classical thermal motion becomes dominant over quantum delocalization for large system size. The significance of anharmonicities in this atomic motion is estimated by comparing with a harmonic approximation for the vibrational modes in graphene bilayers.