A Theoretical Examination of Various Complexes of a Proposed Novel Chemosensor Material—Graphene/SiC

The potential of semiconducting, corrugated graphene, grown on silicon carbide, as an active element in chemosensors is studied in the present work. For this purpose, the adsorption of benzene, diazepam and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) on the material’s surface was modeled. According to the graphene sheet bending and adsorbate–adsorbent distances, the heterostructure favors the ligands in the order of diazepam < benzene < TCDD. The apparent ambiguity in the results for diazepam is easy to explain. The abundance of lone pairs and π-electrons compensates for the low-symmetry, non-planar, far from optimal (adsorption-wise) geometry. The maximum band gap change in the heterostructure, caused by adsorption, is 0.02 eV. Intermolecular binding does not alter the HOMO–LUMO difference in benzene and TCDD by more than 0.01 eV. The completely planar molecules are not expected to undergo significant geometrical changes; hence, the alteration in their frontier orbitals is also minimal. The adsorption of diazepam, however, causes significant changes in the projected density of states of both structures in the complex. In conclusion, corrugated graphene is applicable as an active material in selective chemosensors for non-planar aromatic molecules.