Structures, Stability, Vibration Entropy and IR Spectra of Hydrated Calcium Ion Clusters [Ca(H2O)n]2+ (n=1-20, 27): A Systematic Investigation by Density Functional Theory

The low-lying candidates of hydrated calcium ion clusters, [Ca(H2O)(n)](2+) with n = 1-20 and 27, have been extensively sought by using density functional theory (DFT) at BLYP/6-311+G(d,p) level. The results showed that the first hydration shell around the calcium ion was fully occupied by six water molecules, whereas the second hydration shell might be fully occupied with different numbers of water molecules. This just corresponds to different growth patterns of the hydrated calcium ion clusters. Furthermore, we revealed that the vibration entropy contributed to the free energy of an isomer significantly. As a result, the stability of some low-lying candidates at zero-temperature was not maintained at finite temperatures. Therefore, we suggested that, at finite temperatures, the realistic products of [Ca(H2O)(n)](2+) should be a mixture of the best candidate and some of metastable isomers for a given cluster size. For a cluster having second and/or third shell of water molecules, we found structural transitions between a low-lying structure and the lowest-energy structure undergoing much lower energy barriers. In addition, the IR spectra of the best candidates were predicted, in which the evolution of hydrogen-bond configurations with the cluster size was revealed.