A benchmark quantum chemical study of the stacking interaction between larger polycondensed aromatic hydrocarbons

by Janowski, Tomasz; Pulay, Peter

Large-scale electronic structure calculations were performed for the interaction energy between coronene, C24H12 with circumcoronene, C54H18, and between two circumcoronene molecules, in order to get a picture of the interaction between larger graphene sheets. Most calculations were performed at the SCS-MP2 level but we have corrected them for higher-order correlation effects using a calculation on the coronene-circumcoronene system at the quadratic CI, QCISD(T) level. Our best estimate for the interaction energy between coronene and circumcoronene is 32.1 kcal/mol. We estimate the binding of coronene on a graphite surface to be 37.4 or 1.56 kcal/mol per carbon atom (67.5 meV/C atom). This is also our estimate for the exfoliation energy of graphite. It is higher than most previous theoretical estimates. The SCS-MP2 method which reproduces the CCSD(T) and QCISD(T) values very well for smaller aromatic hydrocarbons, e.g., for the benzene dimer, increasingly overestimates dispersion as the bandgap (the HOMO-LUMO separation) decreases. The barrier to the sliding motion of coronene on circumcoronene is 0.45 kcal/mol, and for two circumcoronene molecules 1.85 kcal/mol (0.018 and 0.034 kcal/mol per C atom, respectively). This means that larger graphenes cannot easily glide over each other.

Journal
Theoretical Chemistry Accounts
Volume
130
Issue
2-3
Year
2011
Start Page
419
ISBN/ISSN
1432-2234; 1432-881X
DOI
10.1007/s00214-011-1009-6