The thermodynamic and kinetic properties of hydrogen dimers on graphene

TL;DR

This study uses ab initio simulations to analyze the thermodynamic and kinetic properties of hydrogen dimers on graphene, revealing isotope effects and matching experimental desorption spectra.

Contribution

It provides detailed insights into hydrogen dimer behavior on graphene, including vibrational energy corrections and isotope effects, which were not previously comprehensively studied.

Findings

Vibrational zero-point energy corrections are significant in kinetics.

Kinetic mobility decreases with increasing hydrogen isotope mass.

Simulated desorption spectra closely match experimental data.

Abstract

The thermodynamic and kinetic properties of hydrogen adatoms on graphene are important to the materials and devices based on hydrogenated graphene. Hydrogen dimers on graphene with coverages varying from 0.040 to 0.111 ML (1.0 ML $= 3.8\times10^{15}$cm$^{-2}$) were considered in this report. The thermodynamic and kinetic properties of H, D and T dimers were studied by ab initio simulations. The vibrational zero-point energy corrections were found to be not negligible in kinetics, varying from 0.038 (0.028, 0.017) to 0.257 (0.187, 0.157) eV for H (D, T) dimers. The isotope effect exhibits as that the kinetic mobility of a hydrogen dimer decreases with increasing the hydrogen mass. The simulated thermal desorption spectra with the heating rate $\alpha = 1.0$ K/s were quite close to experimental measurements. The effect of the interaction between hydrogen dimers on their thermodynamic and kinetic properties were analyzed in detail.