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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Hydroxyl Migration in Heterotrimetallic Clusters: An Assessment of Fluxionality Pathways
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Hydroxyl Migration in Heterotrimetallic Clusters: An Assessment of Fluxionality Pathways

机译:异三金属簇中的羟基迁移:通量路径的评估。

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Water splitting at the unsaturated metal center and subsequent hydroxyl migration are key steps toward successful H2 liberation from cheap and abundant water using transition metal cluster anions. In this report we initiate a theoretical study (DFT) to assess the efficacy of heterometallic cores instead of the widely studied and well established homometallic cores. To accomplish this goal, one tungsten center in W3O6(-) core has been replaced by different transition metals such as titanium, technetium, and osmium. Introduction of the heterometal makes the core asymmetric and electronically anisotropic. To evaluate the efficiency of these heterometallic cores, fluxionality pathways for hydroxyl migration have been studied in detail. We show that the cores W2TcO6(-) (2) and W2OsO6(-) (3) can exhibit fluxionality for hydroxyl migration and thus can potentially facilitate H-2 liberation from H2O. Notably, a new class of low-energy structures generated upon oxide bridge opening process and subsequent structural rearrangement facilitates the hydroxyl migration event. To illustrate the heterometallic effect further, we show that previously inaccessible energy barriers for hydroxyl migration in a homometallic trimolybdenum core become energetically achievable when one of the metals is replaced by a 5d element osmium.
机译:在不饱和金属中心的水分解和随后的羟基迁移是使用过渡金属簇阴离子成功地从廉价和丰富的水中释放H2的关键步骤。在本报告中,我们启动了一项理论研究(DFT)来评估异金属核的功效,而不是经过广泛研究和完善的同金属核。为了实现这一目标,W3O6(-)芯中的一个钨中心已被不同的过渡金属(例如钛,tech和)所取代。引入杂金属使核不对称且具有电子各向异性。为了评估这些杂金属核的效率,已详细研究了羟基迁移的流动性途径。我们表明,核心W2TcO6(-)(2)和W2OsO6(-)(3)可以表现出羟基迁移的流动性,因此可以潜在地促进H-2从H2O释放。值得注意的是,在氧化物桥打开过程和随后的结构重排时产生的新型低能结构促进了羟基迁移事件。为了进一步说明异金属效应,我们显示出,当其中一种金属被5d元素replaced替代时,从能量上可获得在均金属三聚钼芯中无法实现的羟基迁移的能垒。

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