Structures and Solvation Energies Effects Versus Temperature. An MP2 Investigations in the Framework of Cluster Model

结构和溶剂化能随温度的变化:基于簇模型的MP2研究

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Abstract

Structures, relative stabilities, solvation enthalpies, and free energies of the (Be(H2O)n=12)2+ cluster in gas and in water phases were investigated in this work using Moller-Plesset perturbation theory (MP2) and considering a temperature range of 40-400 K. The 12 H(2)O molecules are distributed between the first, second, and third solvation shells. The calculated distances Be2+ - O distances in gas phase are in good agreement with the experimental range which confirms the strong influence of long-distance interactions in cluster stabilization. Structural comparison between gas and water phases shows that the addition of the bulk solvent causes changes in the cation-water bond lengths of few hundredths of angstroms. The obtained solvation free energy of beryllium ion in water at room temperature (298.15 K) results in b - 575.1 kcal mol(-1) in very good agreement with the corresponding experimental counterpart. The computed solvation free energies increase as a polynomial function of the temperature while the change in the solvation enthalpies is found to be negligible.

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