15) When considering the two rings rotated by different angles around the minimum, the calculated energies are always higher than that corresponding to the costrained conformation at 22°.

Articles you may be interested inElectronic structures and water reactivity of mixed metal sulfide cluster anions Coexistence of solvated electron and benzene-centered valence anion in the negatively charged benzenewater clusters J. Chem. Phys. 138, 014310 (2013); 10.1063/1.4773398 Effect of polarizability of halide anions on the ionic solvation in water clusters A collisional approach for the study of electron solvation in water and ammonia clusters and autodetachment of solvated molecular anions AIP Conf. Proc. 298, 528 (1994); 10.1063/1.45413 Photoelectron spectroscopy of iodine anion solvated in water clusters J. Chem. Phys. 95, 9416 (1991);In this paper we present a quantum-mechanical study of anions in water clusters, X-(H 2 0)n (X=Cl, Br, I, and n= 1-6). Molecular orbital calculations at the self-consistent field (SCF) level and at the second-order MQSller-Plesset (MP2) level were performed using extended basis sets. Full structural optimization was conducted at the MP2 level for n = 1 and at the SCF level for n=2-6. The energies and charge distribution of X-(H 2 0) were calculated at the MP2level, while the energies of the X-(H 2 0)n (n=2-6) clusters were calculated at the MP2level using the SCF optimized geometry. Calculations of total and sequential enthalpies of hydration and for the vertical ionization potentials were conducted for X-(H 2 0), the hydrogen bonded and linear isomers of X-(H 2 0h, the pyramidal structure of X-(H 2 0)3' and the interior and surface isomers of X-(H 2 0)n' n=4-6. The calculated hydration enthalpies account well for their experimental size dependence for n = 1-6. However, the isomer specificity of the hydration enthalpies is reflected by a small energy difference (<'>= 1-5 kcal mol-I) between the surface and interior isomers at a fixed n, precluding the assignment of structural isomers on the basis of ground-state energetics. The cluster size dependence and isomer specificity of the calculated vertical ionization potentials in conjunction with experimental data provide a diagnostic tool for the structural assignment of isomers and for the distinction between surface and interior structures. The central prediction emerging from the structure-energetic relations based on cluster size dependence and isomer specificity of vertical ionization potentials, is the prevalence of surface structures for Cl-(H 2 0)n (n=2-6), Br-(H 2 0)n (n=2-6), and I-(H 2 0)n (n=2-5), while a "transition" from surface to interior structure may be exhibited for I-(H 2 0)6'

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