Computational Study of the Zr4+ Tetranuclear Polymer, [Zr4(OH)8(H2O)16]8

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 111; no. 45; pp. 11395 - 11399
• Main Authors: Rao, Niny, Holerca, Marian N, Klein, Michael L, Pophristic, Vojislava
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15.11.2007
• Subjects: Models, Molecular; Polymers - chemistry; Zirconium - chemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp0734880

The Zr4+ tetramer, [Zr4(OH)8(H2O)16]8+, is thought to be the major component of the Zr4+ polymer system in aqueous solution, present as a dominant ionic cluster species compared to other Zr4+ clusters under various experimental conditions. Despite widespread applications of zirconium, the structure and dynamics of the tetramer in aqueous solution are not well understood. We conducted a combination of ab initio molecular dynamics and quantum mechanical studies in the gas phase and aqueous solution and related our results to the available experimental data to provide atom-level information on the behavior of this species in aqueous solution. Our simulations indicate that the tetramer structure is stable on the picosecond time scale in an aqueous environment and that it is of a planar form, comprising eight-coordinated Zr4+ ions with an antiprism/irregular dodecahedron ligand arrangement. In combination with our studies of Zr4+ dimer and trimer clusters, our results provide detailed geometrical information on structural motifs for building zirconium polymers and suggest a possible polymerization path.