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Distorted fivefold coordination of Cu2+(aq) from a Car-Parrinello Molecular Dynamics Simulation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
2005 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 7, no 15, 2874-2880 p.Article in journal (Refereed) Published
Abstract [en]

The solvation shell structure and dynamics of a single Cu2+ ion in a periodic box with 32 water molecules under ambient conditions has been investigated using Car–Parrinello molecular dynamics simulations in a time-window of 18 ps. Five-fold coordination with four equidistant equatorial water molecules at 2.00 and one axial water molecule at 2.45 from the Cu2+ ion is found. A hole without water molecules is found on the opposite side of the axial water. The ion–water bonding character for the equatorial water molecules is different from that of the axial water molecules, as shown by a localized orbital analysis of the electronic structure. Moreover, the calculated OD stretching vibrational band for the equatorial water molecules lies ca. 175 cm–1 below the axial-water band, in good agreement with experimental data. The equatorial-water band lies below, and the axial-water band above, the pure liquid D2O band, also in agreement with experimental data.

Place, publisher, year, edition, pages
2005. Vol. 7, no 15, 2874-2880 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-92890DOI: 10.1039/b502427gOAI: oai:DiVA.org:uu-92890DiVA: diva2:166203
Available from: 2005-04-07 Created: 2005-04-07 Last updated: 2013-09-20Bibliographically approved
In thesis
1. Classical and Car-Parrinello Molecular Dynamics Simulations of Polyvalent Metal Ions in Water
Open this publication in new window or tab >>Classical and Car-Parrinello Molecular Dynamics Simulations of Polyvalent Metal Ions in Water
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The aqueous solvation of metal ions is one of the long-standing and complex problems in chemistry, with implications for and applications in a broad range of biochemical and electrochemical systems, where water is the all-pervasive medium.

This thesis describes computer simulations of Al3+(aq), Fe2+(aq), Fe3+(aq) and Cu2+(aq). Various aspects of the solvation of these polyvalent metal ions in water are addressed, at different levels of theory, using Car-Parrinello molecular dynamics, classical molecular dynamics and quantum-mechanical cluster calculations. Polyvalent metal ions are particularly interesting because of their large influence on the solvent structure, dynamics and thermodynamics, as well as on the properties of the individual solvent molecules. Polyvalent metal ions in aqueous solution also constitute a challenging subject for computer simulations since a sophisticated interaction model is needed to incorporate the large many-body effects.

All the ion-water coordination figures in this thesis are octahedral, except in the Cu2+(aq) solution, where the ion is penta-coordinated with four equatorial neighbours in a plane and one axial neighbour located ~0.45 Å further out from the ion. The equatorial ion-water bonds have covalent character, while the axial water molecule is only electrostatically bound. For all the ions, the OD stretching frequencies of the first-shell water molecules are much more downshifted than in liquid water. In the case of Cu2+(aq), however, only the OD frequencies of the equatorial water molecules are downshifted with respect to bulk water whereas the OD frequencies of the axial water molecule are slightly upshifted.

Various limitations of the Car-Parrinello molecular dynamics simulations have been explored and compared, such as finite system-size effects and shortcomings in the electronic structure calculations. The Car-Parrinello simulations are found to give reasonable descriptions of the polyvalent metal ions in aqueous solution.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2005. vi+39 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 38
Keyword
Inorganic chemistry, Car-Parrinello molecular dynamics simulations, ab initio calculations, ion, copper, aluminium, metal ion, water, aqueous solution, solvation, Oorganisk kemi
National Category
Inorganic Chemistry
Identifiers
urn:nbn:se:uu:diva-5742 (URN)91-554-6211-1 (ISBN)
Public defence
2005-04-29, Polhemsalen, The Ångstrom Laboratory, Lägerhyddsvägen 1, Uppsala, 10:15
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Supervisors
Available from: 2005-04-07 Created: 2005-04-07Bibliographically approved

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Spångberg, DanielHermansson, Kersti

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