Energetics of interlayer binding in graphite: The semiempirical approach revisited

Abstract

We have developed a semiempirical method to obtain interlayer binding energy of graphite in the previous work ͓M. Hasegawa and K. Nishidate, Phys. Rev. B 70, 205431 ͑2004͔͒. In the present paper, we revisit this approach and develop an improved method, in which ab initio calculations based on the density functional theory ͑DFT͒ are also corrected through an empirical atom-atom van der Waals ͑vdW͒ interaction. The local density approximation ͑LDA͒ and generalized gradient approximation ͑GGA͒ are used in the DFT calculations. The parametrized damping function introduced to modify the asymptotic atom-atom vdW interaction is more flexible than the previous ones and covers a wider range of possibility in correcting for the approximate DFT calculations. The damping function is determined empirically by imposing the condition that the experimental interlayer spacing, in-plane lattice constant, and c-axis elastic constant are reproduced. We also require consistency between the LDA-and GGA-based methods ͑LDA+ vdW, GGA+ vdW͒ as the theoretically motivated necessary condition. The interlayer binding energy obtained by this method is 60.4 meV/atom at T = 0 K. The result of ϳ54 meV/atom at room temperature corrected by the thermal effect is consistent with the most recent experiment, 52± 5 eV/atom ͓R. Zacharia et al., Phys. Rev. B 69, 155406 ͑2004͔͒. The atom-atom vdW interaction obtained by the present semiempirical method favorably corrects for the overbinding and underbinding nature of the LDA and GGA, respectively, in the in-plane energetics of graphite. That interaction also provides a useful starting point for the studies of energetics of other graphitic systems such as fullerenes and carbon nanotubes.

Structure and Dynamics of Surfactant and Hydrocarbon Aggregates on Graphite: A Molecular Dynamics Simulation Study

“…This value compares well with those reported from experiments, namely, 43, 57 35, 58 and 52 meV/atom, 59 whereas other theoretical calculations range typically between 20 and 60 meV/atom. [60][61][62][63][64][65][66] It is noteworthy that theoretical values as low as an order of magnitude smaller or as high as 170 meV/ atom have also been reported. For a single hydrocarbon molecule, here C 12 on graphite, the model-predicted adsorption energy at T ) 0 K is 1.3 eV in vacuum.…”

Deformation and transfer doping of a single-walled carbon nanotube adsorbed on metallic substrates

“…This effect is nominal for a small deformation but it is significant for a large enough deformation to make the minimum wall-wall distance comparable to the interlayer separation of graphite. This atomic interaction was obtained by a semiempirical analysis of the interlayer binding of graphite 42,43 and consists of the interaction reproducing the ab initio DFT calculations in the local density approximation ͑LDA͒ and the van der Waals interaction not taken into account in the DFT calculations.…”

Structural, electronic, and magnetic properties of iron carbideFe7C3phases from first-principles theory

“…The interlayer bonding is largely determined by van der Waals interactions, which cannot be correctly described by conventional DFT methods. 42 In recent years, many efforts have been made to calculate the interlayer interaction of layered compounds, including graphite, using other theoretical methods. [42][43][44][45] The diamond phase, though, can be well addressed with the DFT method used in this work.…”