Combined use of DFT based Reactivity Indices and the Non-covalent Index in the Study of Intermolecular Interactions
Conceptual Density Functional Theory (sometimes also called DFT based
reactivity theory or Chemical DFT) has proven to be an ideal framework for
the introduction of chemical reactivity descriptors . These indices are
defined as response functions of the energy E of the system with respect
to either the number of electrons N, the external potential v(r) or both.
These definitions have afforded their non-empirical calculation and
applications in many fields of chemistry have been performed, often
combined with principles such as the electronegativity equalization
principle of Sanderson and Pearson’s hard and soft acids and bases (HSAB)
and maximum hardness principles. In this talk, we focus on recent studies
in which a combined use of these reactivity indices and the Non-Covalent
Interaction (NCI) Index  was carried out in order to scrutinize
intermolecular interactions. In a first part, we focus on halogen bonding.
Halogen bonds between the trifluoromethyl halides CF3Cl, CF3Br and CF3I,
and dimethyl ether, dimethyl sulfide, trimethylamine and trimethyl
phosphine were investigated using the HSAB concept with conceptual DFT
reactivity indices, the Ziegler-Rauk type energy decomposition analysis
, the Natural Orbital for Chemical Valence framework (NOCV) , and
the NCI index. It is found that the relative importance of electrostatic
and orbital (charge transfer) interactions in these halogen bonded
complexes varies as a function of both the donor and acceptor molecules
. Hard and soft interactions were distinguished and characterized by
atomic charges, electrophilicity and local softness indices. Dual
descriptor plots indicate an orbital σ-hole on the halogen similar to the
electrostatic σ-hole manifested in the molecular electrostatic potential.
The characteristic signal found in the reduced density gradient versus
electron density diagram corresponds to the non-covalent interaction
between contact atoms in the NCI plots, which is the manifestation of
halogen bonding within the NCI theory. The unexpected C–X bond
strengthening observed in several cases was rationalized within the MO
In a second part of the talk, we present recent results on the use of the above mentioned quantities in the study of metal-metal interactions .
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Speaker(s) : Frank De Proft, Eenheid Algemene Chemie (ALGC), Vrije Universiteit Brussel (VUB),
Pleinlaan 2, B-1050 Brussels, Belgium
Public : Tous
Date : June 26 2013
Place : Paris
- F. De Proft: Combined use of DFT based Reactivity Indices and the Non-covalent Index in the Study of Intermolecular Interactions
- A. Martín Pendás: Decay rate of delocalization indices: towards a real space image of the insulating or metallic character of a material
- M. Yáñez: Playing around with Beryllium Bonds
- P. Popelier: Quantum Chemical Topology: on Bonds and Force Fields
- W. Yang: Non-Covalent Interaction Analysis in Fluctuating Environments and Exchange-Correlation Energies from Response Properties
- S. J. Grabowski: Non-covalent interactions: characteristics and mechanisms of formation - the topological approach Detailed list
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