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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Structure and Bonding in [W_(10)O_(32)]~(n-) Isopolyanions
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Structure and Bonding in [W_(10)O_(32)]~(n-) Isopolyanions

机译：[W_（10）O_（32）]〜（n-）异聚阴离子的结构和键合

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摘要

The structure and bonding in oxidized and reduced decatungstate anions have been investigated using density-functional methods. The computational-experimental agreement is good for the geometrical parameters of the oxidized species. The electronic structure of the anions has been probed with molecular-orbital, Mulliken-Mayer, and bonding-energy approaches, and the various analyses are in general accordance with spectroscopic evidence and theoretical models. The results have indicated that W-O interactions are largely W d-O p in character, and that σ and π bonds link the metal centers to terminal and bridging (O_(2c)) oxygen atoms. Some W-O_(2c) orbital interactions can be represented as [W_4O_4] or [W_6O_6] closed-loop structures, but these bonding modes have not been found to make a particularly outstanding contribution to the stability of the molecules. Mayer indexes correspond to (fractional) multiple, approximately single, and low-order character for terminal, bridging, and internal bonds, respectively, and the valency analysis has yielded similar bonding capacities for the different oxygen atoms. A distribution of the negative charge over all types of oxygen sites, and metal charges and orbital populations considerably different from the formal assignments have been obtained from the Mulliken analysis. Minor structural changes have been detected in reduced decatungstates, in accord with the general properties of the orbitals occupied by the added electrons.
机译：已使用密度泛函方法研究了氧化的和还原的十碳酸盐阴离子的结构和键合。计算-实验协议对于氧化物种的几何参数是有利的。阴离子的电子结构已通过分子轨道，Mulliken-Mayer和键合能量方法进行了探究，各种分析大体上符合光谱学证据和理论模型。结果表明，W-O相互作用的特征主要是W d-O p，并且σ和π键将金属中心连接到末端和桥接的（O_（2c））氧原子。一些W-O_（2c）轨道相互作用可以表示为[W_4O_4]或[W_6O_6]闭环结构，但尚未发现这些键合模式对分子的稳定性有特别突出的贡献。 Mayer指数分别对应于末端键，桥键和内部键的（分数）多重，近似单个和低阶特征，并且化合价分析已为不同的氧原子产生了相似的键合能力。从Mulliken分析中获得了负电荷在所有类型的氧位点上的分布，以及金属电荷和轨道种群与形式分配的显着不同。根据被添加的电子占据的轨道的一般性质，在还原态下的细小结构变化已被检测到。

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