Simulation of Ir(III) in Aqueous Solution: The Most Inert Ion Hydrate

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Contents Vol 65(12)

doi:10.1071/CH12303

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Chemical Institute

Simulation of Ir(iii) in Aqueous Solution: The Most Inert Ion Hydrate

Philipp A. Pedevilla ^A, Thomas S. Hofer ^A, Bernhard R. Randolf ^A and Bernd M. Rode ^A ^B

^A Theoretical Chemistry Division, Institute of General, Inorganic and Theoretical Chemistry, University of Innsbruck, Innrain 80-82, A-6020 Innsbruck, Austria.
^B Corresponding author. Email: Bernd.M.Rode@uibk.ac.at

Australian Journal of Chemistry 65(12) 1582-1586 http://dx.doi.org/10.1071/CH12303
Submitted: 27 June 2012 Accepted: 31 August 2012 Published: 12 October 2012





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Abstract

The ab initio quantum mechanical charge field (QMCF) molecular dynamics (MD) approach at Hartree-Fock level was used to simulate the tripositive iridium ion in aqueous solution, evaluating structure and dynamics of its hydrate complex. The Ir-OH₂ force constant was of particular interest because of the observed high inertness of Ir(iii) in aqueous solution. Iridium forms three hydration shells. Six water molecules coordinate the ion in the first hydration shell in a well defined octahedral geometry, and no exchanges took place during the simulation time of 15 ps. The second hydration shell is very flexible, however, with a mean residence time of a water molecule of 3.6 ps. The third shell can be identified only by a slight ordering effect. This investigation classified the Ir-OH₂ force constant as the strongest ion-OH₂ bond known to date.

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