Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5375855 | Chemical Physics | 2008 | 9 Pages |
Abstract
The interactions of the simple radicals CH3, NH2, OH, and F with water have been studied by DFT (UB3LYP/6-311++G(2d,2p)) and ab initio (RHF-UCCSD(T)/6-311++G(2d,2p)) methods. In this order the number of lone pairs (from zero to three), the electronegativity, and the strength of the X-H bonds increase (XÂ =Â C, N, and O). The various minima of the radical-water complexes were located using the multiple minima hypersurface (MMH) approach which had previously been proven to be useful for closed-shell molecules. The role of the unpaired electron in hydrogen bonding was investigated using the natural bond orbital (NBO) analysis. A considerable contribution of the unpaired electron to the complex stabilization was only found for the methyl radical and the fluorine atom, whereas in the aminyl and the hydroxyl radical the role of the unpaired electron is negligible.
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Authors
Rachel Crespo-Otero, Elsa Sánchez-GarcÃa, Reynier SuardÃaz, Luis A. Montero, Wolfram Sander,