Electronic structure and chemical bond in naphthalene and anthracene

Abstract

We investigated the electronic structure of crystalline naphthalene and anthracene within the framework of density functional theory including van der Waals interactions (DFT-D). It is established that for better agreement with experimental values it is necessary to use the increased values of the van der Waals radii, which is caused by an overestimated value of the van der Waals interactions in crystalline linear oligoacenes. Utilization of the DFT-D leads to a correct account of the dispersion forces, which results in a high precision of the computed lattice parameters and cohesive energy. Based on the relaxed crystal structures, we have computed the total and deformation electron density and determined the mechanism of chemical bonds formation in crystals of naphthalene and anthracene. It has been established that the chemical bond in molecular crystals is formed under the influence of not only intramolecular but also intermolecular interactions. On the basis of the Mulliken population analysis it was revealed that two C(3) atoms in naphthalene (or C(3) and C(4) in anthracene) have a positive charge and the population of the rest of the carbon atoms increased, as compared with isolated molecule.

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].…”

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

“…(2) interactions, neglecting dipole-quadrupole forces scaling as C 8 R −8 , which might also play a significant role as found before for other related polycyclic aromatic hydrocarbons. 54,55 Finally, we would like to also assess the influence of higherorder terms beyond pair interactions (e.g., interactions between all atom trimers) in the dispersion correction used, as it was recently done for benzene lattice or cohesive energy. 56 All these issues will thus constitute the guide for the next part of the study.…”

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

“…The main aim of these studies is the development of ab initio schemes for further study of complex biological compounds and molecular crystals. One of our tasks is to discover the possibility to apply the parameters, analyzed in the previous work [26], for the study of more complex crystals. We began our study with quite simple objects such as naphthalene and anthracene.…”