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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Two methanes are better than one: A density functional theory study of the reactions of Mo2Oy- (y=2-5) with methane
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Two methanes are better than one: A density functional theory study of the reactions of Mo2Oy- (y=2-5) with methane

机译：两种甲烷优于一种甲烷：Mo2Oy-（y = 2-5）与甲烷反应的密度泛函理论研究

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摘要

The mechanisms of chemical reactions of molybdenum suboxide clusters Mo2On- (n = 2-5) with methane are investigated using B3LYP hybrid density functional theory and polarized basis sets. In particular, we focus on the reactions of the most stable structural isomers of Mo2O2,3,4,5- that lead to single molybdenum species such as HMoO2CH3-, as seen in the recent experimental study of Jarrold and co-workers. We find that, while all experimentally observed products are unfavorable due to the high amount of energy required to cleave the metal oxide, the formation of HMoO2CH3- is least endothermic. Even in this case, the thermodynamics of these reactions is very unfavorable when a single methane is reacted with the metal oxide. However, we find that the sequential addition of two methanes produces HMoO2CH3- (and another neutral molecule whose identity depends on the number of oxygens in the metal oxide) at a much lower thermodynamic cost. Further, the overall reaction barriers are much lower when the second methane adds prior to the Mo2O2,3,4,5- cleavage. The methane addition at each metal center oxidizes the metals to produce a species that is then stable enough to afford the Mo-Mo cleavage.
机译：利用B3LYP混合密度泛函理论和极化基集研究了低氧化钼簇Mo2On-（n = 2-5）与甲烷的化学反应机理。特别是，我们专注于Mo2O2,3,4,5-最稳定的结构异构体的反应，这些反应会导致单一的钼物种（例如HMoO2CH3-），如Jarrold及其同事的最新实验研究所示。我们发现，尽管所有实验观察到的产物由于裂解金属氧化物所需的大量能量都是不利的，但HMoO2CH3-的形成是吸热最少的。即使在这种情况下，当单一甲烷与金属氧化物反应时，这些反应的热力学也非常不利。但是，我们发现按顺序添加两种甲烷可以以低得多的热力学成本产生HMoO2CH3-（以及另一种中性分子，其身份取决于金属氧化物中的氧数）。此外，当第二种甲烷在Mo2O2,3,4,5-裂解之前添加时，总的反应壁垒要低得多。在每个金属中心的甲烷加成将使金属氧化，从而产生一种物种，然后该物种足够稳定以提供Mo-Mo裂解。

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