title: Buckyplates and buckybowls: examining the effects of curvature on π-π interactions.
abstract: π-π interactions are integral to many areas of chemistry, biochemistry, and materials science. Here we use electronic structure theory to analyze how π-π interactions change as the π-systems are curved in model complexes based on coronene and corannulene dimers. Curvature redistributes electronic charge in the π-cloud and creates a dipole moment in these systems, leading to enhanced intermolecular electrostatic interactions in the concave-convex (nested) geometries that are the focus of this work. Curvature of both monomers also has a geometric effect on the interaction by decreasing the average C-C distance between monomers and by increasing the magnitude of both favorable London dispersion interactions and unfavorable exchange-repulsion interactions. Overall, increasing curvature in nested π-π interactions leads to more favorable interaction energies regardless of the native state of the monomers, except at short distances where the most highly curved systems are less favorable as exchange repulsion terms begin to dominate the interaction.
authors.affiliation: Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, 30332-0400, United States.
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Kennedy
authors.forename: Lori A
authors.initials: LA
authors.lastname: Burns
authors.forename: C David
authors.initials: CD
authors.lastname: Sherrill
mesh_terms: D019281:Dimerization; D004583:Electrons; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D011083:Polycyclic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D055672:Static Electricity
chemical_list: D011084:Polycyclic Aromatic Hydrocarbons; D011083:Polycyclic Compounds; C434863:corannulene; C012256:coronene