title: Homolytic versus heterolytic dissociation of alkalimetal halides: the effect of microsolvation.
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(H(2)O)(n) (n=1 to 4). Our results show that the homolytic dissociation energy of the MX(H(2)O)(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.
authors.affiliation: Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus Montilivi, 17071 Girona, Catalonia, Spain.
authors.forename: Sílvia
authors.initials: S
authors.lastname: Osuna
authors.forename: Marcel
authors.initials: M
authors.lastname: Swart
authors.forename: Evert Jan
authors.initials: EJ
authors.lastname: Baerends
authors.forename: F Matthias
authors.initials: FM
authors.lastname: Bickelhaupt
authors.forename: Miquel
authors.initials: M
authors.lastname: Solà