Periodic Projector Augmented Wave Density Functional Calculations on the Hexachlorobenzene Crystal and Comparison with the Experimental Multipolar Charge Density Model
- Author(s)
- Emmanuel Aubert, Sebastian Lebegue, Martijn Marsman, Thai Thanh Thu Bui, Christian Jelsch, Slimane Dahaoui, Enrique Espinosa, János G. Angyan
- Abstract
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(s)
- Computational Materials Physics
- External organisation(s)
- Université de Lorraine
- Journal
- The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
- Volume
- 115
- Pages
- 14484-14494
- No. of pages
- 11
- ISSN
- 1089-5639
- DOI
- https://doi.org/10.1021/jp206623x
- Publication date
- 2011
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103018 Materials physics
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/d3f3aa62-a9da-43a5-8a52-2ac9f0a18b62