Periodic Projector Augmented Wave Density Functional Calculations on the Hexachlorobenzene Crystal and Comparison with the Experimental Multipolar Charge Density Model

Autor(en)

Emmanuel Aubert, Sebastian Lebegue, Martijn Marsman, Thai Thanh Thu Bui, Christian Jelsch, Slimane Dahaoui, Enrique Espinosa, János G. Angyan

Abstrakt

The projector augmented wave (PAW) methodology has been used to calculate a high precision electron density distribution rho(r) for the hexachlorobenzene crystal phase. Implementing the calculation of the crystallographic structure factors in the VASP code has permitted one to obtain the theoretical multipolar rho(r). This electron density is compared with both the DFT electron density and the experimental multipolar model obtained from high-resolution X-ray diffraction data. This comparison has been carried out in intra- and intermolecular regions within the framework of the quantum theory of atoms-in-molecules (QTAIM) developed by Bader and co-workers. The characterization of the electron density in both C-CI and Cl center dot center dot center dot Cl regions, as well as within the atomic basins, shows similar features for the three models. As a consequence, the observation of charge depletion and charge concentration regions around the halogen nuclei (along the C-Cl bonding axis and in the perpendicular plane, respectively) underlines the nature of halogen bonding in terms of electrophilic and nucleophilic interactions.

Organisation(en)

Computergestützte Materialphysik

Externe Organisation(en)

Université de Lorraine

Journal

The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

Band

115

Seiten

14484-14494

Anzahl der Seiten

11

ISSN

1089-5639

DOI

https://doi.org/10.1021/jp206623x

Publikationsdatum

2011

Peer-reviewed

Ja

ÖFOS 2012

103018 Materialphysik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/d3f3aa62-a9da-43a5-8a52-2ac9f0a18b62