Direct evidence of orbital mixing between water and solvated transition-metal ions: An oxygen 1s XAS and DFT study of aqueous systems

Lars Åke Näslund, Matteo Cavalleri, Hirohito Ogasawara, Anders Nilsson, Lars G.M. Petterson, Philippe Wernet, David C. Edwards, Magnus Sandström, Satish Chandra Babu Myneni

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Abstract

We have studied the chemical bonding of water in the first hydration sphere to transition-metal ions in aqueous solutions by using X-ray absorption spectroscopy (XAS) combined with density functional theory calculations (DFT). The experimental technique is for the first time applied to the study of the oxygen K-edge absorption of liquid water in the presence of dissolved ions. We successfully resolved the electronic structure of water in the first hydration sphere. Features in the oxygen 1s XAS pre-edge region in Cr3+ and Fe3+ solutions are interpreted as mixing between the molecular orbitals of water and the open d shell of the transition-metal ion. These features are absent for Al3+ solutions. Effects on the electronic structure from anions in the first hydration sphere are also described.

Original languageEnglish (US)
Pages (from-to)6869-6876
Number of pages8
JournalJournal of Physical Chemistry A
Volume107
Issue number35
DOIs
StatePublished - Sep 4 2003

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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    Näslund, L. Å., Cavalleri, M., Ogasawara, H., Nilsson, A., Petterson, L. G. M., Wernet, P., Edwards, D. C., Sandström, M., & Myneni, S. C. B. (2003). Direct evidence of orbital mixing between water and solvated transition-metal ions: An oxygen 1s XAS and DFT study of aqueous systems. Journal of Physical Chemistry A, 107(35), 6869-6876. https://doi.org/10.1021/jp034296h