First-Principles Study of the Interaction of Atomic and Molecular Chlorine with Graphene, Silicene, Phosphorene, and h-BN Monolayer

Authors

Mukesh K. Choudhary, Michigan Technological UniversityFollow
Ashima Rawat, University of Colorado Boulder
Lokanath Patra, Georgia Institute of Technology
Ravindra Pandey, Michigan Technological UniversityFollow

Document Type

Article

Publication Date

3-21-2025

Department

Department of Physics

Abstract

The environmental stability of 2D monolayers is critical for their applications across various technology-related fields. These monolayers can degrade when exposed to gaseous components in the environment, so minimizing these degrading effects is essential. In this paper, chlorine exposure to the 2D monolayers, specifically graphene, silicene, phosphorene, and h-BN monolayer, is investigated using van der Waals corrected density functional theory. The results find that atomic chlorine chemisorbs on graphene, h-BN, silicene, and phosphorene with adsorption energies of −1.09, −0.65, −3.10, and −1.74 eV/atom, and bond distances of 3.0, 2.6, 2.2, and 2.1 Å, respectively. In contrast, molecular Cl₂ exhibits physisorption with adsorption energies around −0.22 eV and bond distances ranging from 3.3 to 3.6 Å. NEB calculations show that Cl₂ dissociative chemisorption is exothermic on buckled monolayers (silicene and phosphorene) and endothermic on planar monolayers (graphene and h-BN). On buckled surfaces, Cl₂ dissociates after overcoming energy barriers of 2.0 eV for silicene and 3.2 eV for phosphorene, forming a stable chemisorbed state that is 0.9 eV lower than the physisorbed state. However, on planar monolayers, Cl₂ remains in the physisorbed state because the dissociated chemisorbed state is ≈ 1.5 eV higher in energy. These differences are due to the weaker π-bonds in buckled monolayers, which make dissociation easier, while planar monolayers stabilize the molecular form.

Publisher's Statement

Publisher's record: https://doi.org/10.1021/acsomega.5c01346

Copyright © 2025 The Authors.

Publication Title

ACS Omega

Recommended Citation

Choudhary, M. K., Rawat, A., Patra, L., & Pandey, R. (2025). First-Principles Study of the Interaction of Atomic and Molecular Chlorine with Graphene, Silicene, Phosphorene, and h-BN Monolayer. ACS Omega, 10(12), 11643-12723. http://doi.org/10.1021/acsomega.5c01346
Retrieved from: https://digitalcommons.mtu.edu/michigantech-p2/1574

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial-No Derivative Works 4.0 International License.