Nature of the water/aromatic parallel alignment interactions |
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| Authors: | Mariusz P Mitoraj Goran V Janjić Vesna B Medaković Dušan Ž Veljković Artur Michalak Snežana D Zarić Miloš K Milčić |
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| Affiliation: | 1. Faculty of Chemistry, Department of Theoretical Chemistry, Jagiellonian University, Krakow, Poland;2. Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Belgrade, Serbia;3. Department of Chemistry, University of Belgrade, Belgrade, Serbia;4. Department of Chemistry, Texas A & M University at Qatar, Doha, Qatar |
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| Abstract: | The water/aromatic parallel alignment interactions are interactions where the water molecule or one of its O? H bonds is parallel to the aromatic ring plane. The calculated energies of the interactions are significant, up to ΔECCSD(T)(limit) = ?2.45 kcal mol?1 at large horizontal displacement, out of benzene ring and CH bond region. These interactions are stronger than CH···O water/benzene interactions, but weaker than OH···π interactions. To investigate the nature of water/aromatic parallel alignment interactions, energy decomposition methods, symmetry‐adapted perturbation theory, and extended transition state‐natural orbitals for chemical valence (NOCV), were used. The calculations have shown that, for the complexes at large horizontal displacements, major contribution to interaction energy comes from electrostatic interactions between monomers, and for the complexes at small horizontal displacements, dispersion interactions are dominant binding force. The NOCV‐based analysis has shown that in structures with strong interaction energies charge transfer of the type π → σ*(O? H) between the monomers also exists. © 2014 Wiley Periodicals, Inc. |
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| Keywords: | water/aromatic parallel interactions supramolecular method energy decomposition SAPT NOCV ETS |
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