Properties of crystalline coronene: Dispersion forces leading to a larger van der Waals radius for carbon

Abstract

We investigated the electronic structure of crystalline coronene within the framework of the dispersion corrected density‐functional theory (DFT‐D). We use the DFT‐D2 and DFT‐D3 methods. Utilization of the DFT‐D3 leads to a correct account of the dispersion forces, which results in a good agreement of the computed lattice parameters and cohesive energy. In the framework of DFT‐D3 the cohesive energy of crystalline coronene is 1.483 eV. Computed lattice constants and cohesive energy show good agreement with experimental data if larger van der Waals (vdW) radius for carbon is used. Based on the relaxed crystal structures, we have computed the band structure, total and deformation electron density.

Determining the cohesive energy of coronene by dispersion-corrected DFT methods: Periodic boundary conditions vs. molecular pairs

“…However, what seems to have a more pronounced effect is the use of the PBE or the BLYP functional (compare PBE-D2/MTCP and BLYP-D2/MTCP). Whereas the former slightly underestimates the (averaged) experimental value by up to 14 kJ/mol, although agrees well with other estimates in the literature using the same PBE-D2 scheme, 51 the latter overestimates the experimental value by around 15 kJ/mol. These values are thus, broadly speaking, under-or overestimating the experimental value by around 3 kcal/mol.…”

First principles study of the electronic structure and phonon dispersion of naphthalene under pressure

“…When studying naphthalene, anthracene, coronene, perylene [15,[55][56][57], we used experimental values of vdW radii [58] to obtain the correct values of lattice parameters and cohesive energy. We have established that it was caused by overlapping of carbon p-orbitals [57].…”

Coarse-grained electrostatic interactions of coronene: Towards the crystalline phase

“…The absolute is used because the sign does not influence the pair potential defined in Eq. (13). The values of Q * resulting from density functional calculations performed in Ref.…”

“…A common compromise consists in using static partial charges distributed among the atoms of the underlying microscopic model in the coarse-graining procedure. 8 By implication, as shown in previous studies involving quantum-chemical calculations, 13 it is generally not sufficient to use the static atomic partial charges characterizing an isolated dimer (except for selected configurations such as a parallel displaced one 45 ). However, for static partial charges an angle and temperature dependent coarse-grained pair potential for perylene, a flat but non-discotic molecule, was already developed by Babadi et al 8 using constrained steered dynamics for specific configurations desired to fit an ellipsoidal soft-potential.…”