Halogen bonding, a noncovalent interaction between a halogen atom and a nucleophilic site, is receiving a growing attention in the chemical community stimulating a large number of theoretical investigations. The density functional theory (DFT) approach revealed to be one of the most suitable methods owing to its accuracy and low computational cost. We report here a detailed analysis of the performance of an extensive set of DFT functionals in reproducing accurate binding energies and topological properties for the halogen-bonding interaction of either NCX or PhX molecules (X = F, Cl, Br, I) with the aromatic system of benzene in the T-shaped configuration. It was found that the better performance for both sets of properties is provided by a small subset of functionals able to take into account, implicitly or explicitly (by inclusion of an additive pairwise potential), the dispersion contribution, that is, (omega B97X, M06-2X, M11, mPW2PLYP-D, and B2PLYP-D3.

Assessment of DFT Functionals for QTAIM Topological Analysis of Halogen Bonds with Benzene / A. Forni, S. Pieraccini, D. Franchini, M. Sironi. - In: JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY. - ISSN 1089-5639. - 120:45(2016), pp. 9071-9080. [10.1021/acs.jpca.6b07578]

Assessment of DFT Functionals for QTAIM Topological Analysis of Halogen Bonds with Benzene

A. Forni
;
S. Pieraccini
Secondo
;
D. Franchini
Penultimo
;
M. Sironi
Ultimo
2016

Abstract

Halogen bonding, a noncovalent interaction between a halogen atom and a nucleophilic site, is receiving a growing attention in the chemical community stimulating a large number of theoretical investigations. The density functional theory (DFT) approach revealed to be one of the most suitable methods owing to its accuracy and low computational cost. We report here a detailed analysis of the performance of an extensive set of DFT functionals in reproducing accurate binding energies and topological properties for the halogen-bonding interaction of either NCX or PhX molecules (X = F, Cl, Br, I) with the aromatic system of benzene in the T-shaped configuration. It was found that the better performance for both sets of properties is provided by a small subset of functionals able to take into account, implicitly or explicitly (by inclusion of an additive pairwise potential), the dispersion contribution, that is, (omega B97X, M06-2X, M11, mPW2PLYP-D, and B2PLYP-D3.
hybrid density functionals; generalized gradient approximation; electron-density; charge-density; noncovalent interactions; thermochemical kinetics; dispersion corrections; adjustable-parameters; binding-affinity; hydrogen-bond
Settore CHIM/02 - Chimica Fisica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/470822
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