Physisorption of benzene derivatives on graphene : Critical roles of steric and stereoelectronic effects of the substituent

Research output: Journal Publications and ReviewsRGC 21 - Publication in refereed journalpeer-review

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Original languageEnglish
Pages (from-to)12185-12193
Journal / PublicationPhysical Chemistry Chemical Physics
Issue number18
Online published10 Apr 2015
Publication statusPublished - 14 May 2015


A series of benzene derivatives with different substituents adsorbed on graphene was investigated using a density-functional tight-binding method with a dispersion correction. Compared to benzene, the derivative with either an electron-withdrawing or -donating substituent exhibits stronger physisorption. Moreover, the steric size of the substituent is important in determining the adsorption strength, while the direction and the number of H atoms in the substituent affect the electron transfer from graphene. NBO analysis reveals that the stereoelectronic effect of the conjugation between the substituent and the benzene ring strongly influences the π⋯π interaction region between the molecule and graphene. The findings can deepen the understanding of the interaction between an aromatic molecule and graphene as well as the corresponding adsorption mechanism.