title: Computational Study of the Small Zr(IV) Polynuclear Species.
abstract: Despite widespread zirconium use ranging from nuclear technology to antiperspirants, important aspects of its solvation chemistry, such as the nature of small zirconium(IV) hydroxy cluster ions in aqueous solution, are not known due to the complexity of the zirconium aqueous chemistry. Using a combination of Car-Parrinello molecular dynamics simulations and conventional quantum mechanical calculations, we have determined the structural characteristics and analyzed the aqueous solution dynamics of the two smallest zirconium(IV) cluster species possible, i.e., the dimer and trimer. Our study points to and provides detailed geometrical information for a stable structural motif for building zirconium polymers, the Zr(OH)2Zr bridging unit with 7-8 coordinated Zr ions, which, however, cannot be used to construct a stable structure for the trimer. We find that a stacked trimer, not featuring this motif, is a possible structure, though not a very stable one, shedding new light on this species, and its possible importance in the aqueous chemistry of Zr(4+) ion.
authors.affiliation: Department of Chemistry & Biochemistry and the West Center for Computational Chemistry and Drug Design, University of the Sciences in Philadelphia, Philadelphia, Pennsylvania 19104, and Colgate Palmolive Company, Global Technology Center, Piscataway, New Jersey 08854.
authors.forename: Niny
authors.initials: N
authors.lastname: Rao
authors.affiliation: Department of Chemistry & Biochemistry and the West Center for Computational Chemistry and Drug Design, University of the Sciences in Philadelphia, Philadelphia, Pennsylvania 19104, and Colgate Palmolive Company, Global Technology Center, Piscataway, New Jersey 08854.
authors.forename: Marian N
authors.initials: MN
authors.lastname: Holerca
authors.affiliation: Department of Chemistry & Biochemistry and the West Center for Computational Chemistry and Drug Design, University of the Sciences in Philadelphia, Philadelphia, Pennsylvania 19104, and Colgate Palmolive Company, Global Technology Center, Piscataway, New Jersey 08854.
authors.forename: Vojislava
authors.initials: V
authors.lastname: Pophristic