Institute of Surface Chemistry and Catalysis, University of Ulm , Albert-Einstein-Allee 47, 89069 Ulm, Germany.
Nano Lett. 2013;13(11):5549-55. doi: 10.1021/nl4031456. Epub 2013 Oct 28.
The interaction of ligand-free manganese oxide nanoclusters with water is investigated, aiming at uncovering phenomena which could aid the design of artificial water-splitting molecular catalysts. Gas phase measurements in an ion trap in conjunction with first-principles calculations provide new mechanistic insight into the water splitting process mediated by bi- and tetra-nuclear singly charged manganese oxide clusters, Mn2O2(+) and Mn4O4(+). In particular, a water-induced dimensionality change of Mn4O4(+) is predicted, entailing transformation from a two-dimensional ring-like ground state structure of the bare cluster to a cuboidal octa-hydroxy-complex for the hydrated one. It is further predicted that the water splitting process is facilitated by the cluster dimensionality crossover. The vibrational spectra calculated for species occurring along the predicted pathways of the reaction of Mn4O4(+) with water provide the impetus for future explorations, including vibrational spectroscopic experiments.
研究了配体自由的氧化锰纳米团簇与水的相互作用，旨在揭示有助于设计人工水分解分子催化剂的现象。在离子阱中进行的气相测量与第一性原理计算相结合，为双核和四核单电荷氧化锰团簇 Mn2O2(+)和 Mn4O4(+)介导的水分解过程提供了新的机理见解。特别是，预测了 Mn4O4(+)的水诱导维度变化，涉及到从裸露团簇的二维环状基态结构到水合的八面体羟基配合物的转变。进一步预测，簇维度交叉使水分解过程变得更容易。对于在 Mn4O4(+)与水反应的预测途径中出现的物种的振动光谱的计算，为未来的探索提供了动力，包括振动光谱实验。
