Isotopic effects in structural properties of graphene

TL;DR

This study investigates isotopic effects on the structural properties of graphene using path-integral molecular dynamics, revealing significant quantum effects on interatomic distances and in-plane area, with differences larger than in 3D carbon materials.

Contribution

It provides the first detailed quantification of isotopic effects on graphene's structural properties considering anharmonic and quantum effects.

Findings

Isotopic substitution causes measurable changes in C--C distances.

Quantum effects significantly influence graphene's structural parameters.

Anharmonicity impacts vibrational amplitudes and internal energy.

Abstract

Isotopic effects are relevant to understand several properties of solids, and have been thoroughly analyzed along the years. These effects may depend on the dimensionality of the considered solid. Here we assess their magnitude for structural properties of graphene, a paradigmatic two-dimensional material. We use path-integral molecular dynamics simulations, a well-suited technique to quantify the influence of nuclear quantum effects on equilibrium variables, especially in cases where anharmonic effects are important. Emphasis is put on interatomic distances and mean-square displacements, as well as on the in-plane area of the graphene layer. At low temperature, the relative difference in C--C distance for $^{13}$C and $^{14}$C, with respect to $^{12}$C, is found to be $-2.5$ and $-4.6 \times 10^{-4}$, respectively, larger than in three-dimensional carbon-based materials such as diamond. For the in-plane area, the relative changes amount to $-3.9$ and $-6.9 \times 10^{-4}$. The magnitude of anharmonicity in the lattice vibrations is estimated by comparing the internal energy and atomic vibrational amplitudes with those derived from a harmonic approximation.