Properties and nature of interactions in Cl−(H2O)nn=1,6 clusters: a theoretical study

Abstract A series of Cl − (H 2 O) n complexes has been studied using ab initio post-Hartree–Fock methods. The arrangement of water molecules around the chloride ion in the Cl − (H 2 O) n clusters reveals the competition between the solvation of an anion and the hydrogen bonding between solvent molecules. The larger studied clusters ( n =5,6) possess water molecules in the second solvation shell. Experimental electron affinities together with experimental dissociation energies of ionic clusters were used to estimate the properties of neutral Cl(H 2 O) n complexes. The partitioning of the interaction energies in ionic Cl − (H 2 O) n clusters indicates the dominant character of the electrostatic forces.

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