Role and Effective Treatment of Dispersive Forces in Materials: Polyethylene and Graphite Crystals as Test Cases

A semiempirical addition of dispersive forces to conventional density functionals (DFT-D) has been implemented into a pseudopotential plane-wave code. Test calculations on the benzene dimer reproduced the results obtained by using localized basis set, provided that the latter are corrected for the basis set superposition error. By applying the DFT-D/plane-wave approach a substantial agreement with experiments is found for the structure and energetics of polyethylene and graphite. two typical solids that are badly described by standard local and semilocal density functionals. (C) 2008 Wiley Periodicals, Inc. J Comput Chem 30: 934-939, 2009