Intermolecular π–π interactions in solids

Abstract

A parameter-free DFT/CCSD(T) correction scheme is proposed for precise calculations (close to CCSD(T) accuracy) of weakly bound molecular solids. The correction scheme has been tested for solid benzene and graphite. The CCSD(T)/CBS correction to planewave DFT calculations reproduces the experimentally determined lattice constants for solid benzene. The calculated cohesive energy of benzene (457 meV per molecule) compares well with the experimental values of the heat of sublimation (460–560 meV per molecule). For graphite, the correction yields structural parameters (a = 2.46 Å, c = 6.60 Å) in good agreement with experiment (a = 2.46 Å, c = 6.67 Å). The calculated exfoliation energy of 54 meV per atom agrees fairly well with the most recent experimental value of 52 ± 5 meV per atom.