Vibrational Spectroscopy of Small Hydrated CuOH+ Clusters

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• 作者：Brett M. Marsh ; Jia Zhou ; Etienne Garand
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：March 20, 2014
• 年：2014
• 卷：118
• 期：11
• 页码：2063-2071
• 全文大小：457K
• 年卷期：v.118,no.11(March 20, 2014)
• ISSN：1520-5215

文摘

Coordinated copper hydroxide centers can play an important role in copper catalyzed water oxidation reactions. To have a better understanding of the interactions involved in these complexes, we studied the vibrational spectra of D₂ tagged CuOH⁺(H₂O)_n clusters in the OH stretch region. These clusters are generated by electrospray ionization and probed via cryogenic ion vibrational spectroscopy. The results show that the copper center in the n = 3 clusters has a distorted square planar geometry. The coordination in CuOH⁺(H₂O)_n is therefore more akin to Cu²⁺(H₂O)_n with four ligands in the first solvation shell than Cu⁺(H₂O)_n with two ligands in the first solvation shell. There is also no evidence of any strong axial ligand interactions. The well-resolved experimental spectra enabled us to point out some discrepancies in the calculated spectra, which were found to be highly dependent on the level of theory used.