Structures, energetics, and spectra of hydrated hydroxide anion clusters.
The structures, energetics, electronic properties, and spectra of hydrated hydroxide anions are studied using density functional and high level ab initio calculations. The overall structures and binding energies are similar to the hydrated anion clusters, in particular, to the hydrated fluoride anion clusters except for the tetrahydrated clusters and hexahydrated clusters. In tetrahydrated system, tricoordinated structures and tetracoordinated structures are compatible, while in pentahydrated systems and hexahydrated systems, tetracoordinated structures are stable. The hexahydrated system is similar in structure to the hydrated chloride cluster. The thermodynamic quantities (enthalpies and free energies) of the clusters are in good agreement with the experimental values. The electronic properties induced by hydration are similar to hydrated chloride anions. The charge-transfer-to-solvent energies of these hydrated-hydroxide anions are discussed, and the predicted ir spectra are used to explain the experimental data in terms of the cluster structures. The low-energy barriers between the conformations along potential energy surfaces are reported.
Lee
Han Myoung
HM
National Creative Research Initiative Center for Superfunctional Materials, Department of Chemistry, Division of Molecular and Life Sciences, Pohang University of Science and Technology, San 31, Hyojadong, Namgu, Pohang 790-784, Korea. abcd01@postech.ac.kr
Tarkeshwar
P
P
Kim
Kwang S
KS
D000838:Anions; D003198:Computer Simulation; D004735:Energy Transfer; D006878:Hydroxides / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D012996:Solutions; D013057:Spectrum Analysis; D014867:Water / Q000737:chemistry*
D000838:Anions; D006878:Hydroxides; D012996:Solutions; D014867:Water; D017665:Hydroxyl Radical; C031356:hydroxide ion