Attractive halogen–halogen interactions: F3CCl?FH and F3CCl?FCH3 dimers |
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Authors: | S?awomir J Grabowski Andrzej J Sadlej W Andrzej Sokalski Jerzy Leszczynski |
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Institution: | 1. Department of Physics and Chemistry, University of ?ód?, ul. Pomorska 149/153, PL-90 236 ?ód?, Poland;2. Department of Quantum Chemistry, Institute of Chemistry, Nicolaus Copernicus University, PL-87100 Toruń, Poland;3. Institute of Physical and Theoretical Chemistry, Wroc?aw University of Technology, Wybrze?e Wyspiańskiego 27, PL-50 370 Wroc?aw, Poland;4. Computational Center for Molecular Structure and Interactions, Department of Chemistry, Jackson State University, Jackson MS 39217, USA |
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Abstract: | The F3CCl?FH and F3CCl?FCH3 dimers, which feature the halogen–halogen contacts, are investigated at MP2/6–311++G(d,p) and MP2/aug–cc–pVDZ levels of approximation. The binding energies of these complexes are found to be comparable to those of the weak hydrogen bonds. In both complexes the Cl?F are found to be significantly shorter than the sum of the corresponding van der Waals radii. The C–Cl?F contacts are also found to exhibit certain deviation from linearity. However, the energy differences between linear and bent structures are very small and primarily accounted for by electrostatic interactions between remote parts of the dimer. This indicates a high conformational flexibility of the halogen–halogen contacts and may help to explain the diversity of structural features in crystals formed by halogen-containing molecules. In both dimers the halogen–halogen interaction leads to certain shortening of the C–Cl electron accepting bond. This is accompanied by a small increase of the C–Cl stretching frequency. Hence, the two investigated dimers can possibly be classified as the blue-shifting halogen–halogen contacts. |
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Keywords: | Halogen&ndash halogen interactions Blue-shifting interhalogen interactions Interaction energy decomposition |
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