Journal article
Halogen Bonds: Benchmarks and Theoretical Analysis
Journal of Chemical Theory and Computation, Vol.9(4), pp.1918-1931
Apr/2013
Abstract
We carried out an extensive survey of wave function and DFT methods to test their accuracy on geometries and dissociation energies of halogen bonds (XB). For that purpose, we built two benchmark sets (XB18 and XB51). Between the DFT methods, it was found that functionals with high exact exchange or long-range corrections were suitable for these dimers, especially M06-2X, omega B97XD, and double hybrids. Dispersion corrections tend to be detrimental, in spite of the fact that XB is considered a noncovalent interaction. Wave function techniques require heavy correlated methods (i.e., CCSD(T)) or parametrized ones (SCS-MP2 or SCS(MI)MP2). Heavy basis sets are needed to obtain high accuracy, such as aVQZ or aVTZ+CP, and ideally a CBS extrapolation. Relativistic ECPs are also important, even for the bromine based dimers. In addition, we explored some XB with new theoretical tools, the NCI ("Non-Covalent Interactions") method and the NOFF ("Natural Orbital Fukui Functions").
Details
- Title
- Halogen Bonds; Benchmarks and Theoretical Analysis
- Creators
- Sebastian Kozuch (null) - The Weizmann Institute of ScienceJan M. L. Martin (null) - The Weizmann Institute of Science
- Resource Type
- Journal article
- Publication Details
- Journal of Chemical Theory and Computation, Vol.9(4), pp.1918-1931; Apr/2013
- Number of pages
- 14
- Language
- English
- DOI
- https://doi.org/10.1021/ct301064t
- Grant note
- Weizmann Institute; Weizmann AERI (Alternative Energy Research Initiative); University of North TexasS.K. was supported by a Koshland Fellowship from the Weizmann Institute. During the course of the research, J.M.L.M. was on leave of absence as the Thatcher Professor of Chemistry at the Weizmann Institute of Science. This research was supported in part by the Weizmann AERI (Alternative Energy Research Initiative) and by a startup grant from the University of North Texas. The authors would like to thank Prof. Milko E. van der Boom for introducing us to this topic and Dr. Jean-Francois Lamere for preliminary calculations._ALMAME_DELIMITER_
- Record Identifier
- 993264971503596
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