Graduation Term


Document Type


Degree Name

Master of Science (MS)


Department of Chemistry

Committee Chair

Bhaskar Chilukuri


Halogen· · · halogen (X· · ·X) bonds are a poorly understood, special class of non-covalent contact known to profoundly impact processes of molecular self-assembly, such as crystal formationand thin-layer epitaxy. The study of X· · ·X bonding on surfaces is well established, but it is unclear exactly to what extent a surface influences X· · ·X contacts or their dynamics. Simulations of X· · ·X bonding at ordered surfaces via plane-wave density functional theory (DFT) occasionally arise to compliment experimental results, but there is yet to be a comprehensive in silico exploration probing the nature of the X· · ·X bond at surface interfaces. This thesis reports—to the best of this author’s knowledge—the first multimodal, comprehensive in silico approach to elucidating the nature of the X· · ·X bond on 2D surfaces. Both molecular and plane-wave DFT are used to probe X· · ·X energetics and electronic structure in model haloarene systems on highly oriented-pyrolytic graphite (HOPG) and (111) cross-sections of the noble metals (i.e. Au(111), Ag(111), and Cu(111) surfaces). Deep insights on the nature of X· · ·X bonding on HOPG are reported, and curiosities about X· · ·X bonding at noble metal surfaces are explored.


Page Count


Available for download on Saturday, May 31, 2025