Potassium intercalation in graphite is investigated by first-principles theory. The bonding in the potassium-graphite compound is reasonably well accounted for by traditional semilocal density-functional theory (DFT) calculations. However, to investigate the intercalate formation energy from pure potassium atoms and graphite requires use of a description of the graphite interlayer binding and thus a consistent account of the nonlocal dispersive interactions. This is included seamlessly with ordinary DFT by a van der Waals density-functional (vdW-DF) approach [M. Dion et al., Phys. Rev. Lett. 92, 246401 (2004)]. The use of the vdW-DF is found to stabilize the graphite crystal, with crystal parameters in fair agreement with experiments. For graphite and potassium-intercalated graphite, structural parameters such as binding separation, layer binding energy, formation energy, and bulk modulus are reported. Also, the adsorption and subsurface potassium absorption energies are reported. The vdW-DF description, compared with the traditional semilocal approach, is found to weakly soften the elastic response.

• Received 18 April 2007

DOI:https://doi.org/10.1103/PhysRevB.76.155425