Homolytic versus Heterolytic Dissociation of Alkalimetal Halides: The Effect of Microsolvation |
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| Authors: | Sílvia Osuna Marcel Swart Dr. Evert Jan Baerends Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Miquel Solà Prof. Dr. |
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| Affiliation: | 1. Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia (Spain), Fax: (+34)?972‐41‐83‐56;2. Institució Catalana de Recerca i Estudis Avan?ats (ICREA), 08010 Barcelona (Spain);3. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, Scheikundig Laboratorium der Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam (The Netherlands), Fax: (+31)?20‐59‐87‐629;4. Department of Chemistry, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang, 790‐784 (South Korea) |
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| Abstract: | Herein we report density functional calculations of homolytic and heterolytic dissociation energies of the diatomic alkalimetal halides MX (M=Li, Na, K, Rb, and Cs and X=F, Cl, Br, I, and At) and their corresponding microsolvated structures MX?(H2O)n (n=1 to 4). Our results show that the homolytic dissociation energy of the MX?(H2O)n species increases with the number of water molecules involved in the microsolvated salts. On the other hand, the heterolytic dissociation energy follows exactly the opposite trend. As a result, while for the isolated diatomic alkalimetal halides, homolytic dissociation is always favored over heterolytic dissociation, the latter is preferred for CsF and CsCl already for n=2, and for n=4 it is the preferential mode of dissociation for more than half of the species studied. |
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| Keywords: | ab initio calculations alkali metals density functional calculations halides solvent effects |
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