Interaction of Dioxygen with Al Clusters and Al(111): A Comparative Theoretical Study
Interaction of Dioxygen with Al Clusters and Al(111): A Comparative Theoretical Study
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DOI：
10.1021/jp711991b
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发表时间：
2008-04
影响因子：
3.7
通讯作者：
C. Mosch;Constantine Koukounas;N. Bacalis;A. Metropoulos;A. Gross;A. Mavridis
中科院分区：
文献类型：
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作者：
C. Mosch;Constantine Koukounas;N. Bacalis;A. Metropoulos;A. Gross;A. Mavridis
我们使用基于波函数的量子化学方法和密度泛函理论（DFT）研究了氧分子与Al簇和Al（111）的相互作用。这些计算的动机是分子束实验表明O2在Al（111）上的吸附应该被激活，而周期性DFT计算得出几乎所有O2在Al（111）上的冲击构型的纯吸引吸附路径。在小的Al4簇上，精确的基于波函数的量子化学方法在O2吸附中发现了一个不消失的屏障。平板和较大Al团簇的DFT计算证实了自旋效应对Al上O2解离势垒的重要作用。结果表明，交换相关效应对O2/Al体系中吸附势垒的测定起着至关重要的作用，但它们的测定受到了严重的技术问题的阻碍，并进行了详细的讨论。
We have studied the interaction of an oxygen molecule with Al clusters and Al(111) using both wave-function-based quantum chemistry methods and density functional theory (DFT). These calculations were motivated by the fact that molecular beam experiments indicate that the adsorption of O2 on Al(111) should be activated whereas periodic DFT calculations yield purely attractive adsorption paths for almost all impact configurations of O2 on Al(111). On small Al4 clusters, accurate wave-function-based quantum chemistry methods find a non-vanishing barrier in the O2 adsorption. The DFT calculations for slabs and larger Al clusters confirm the important role of spin effects for the O2 dissociation barrier on Al. The results indicate that exchange-correlation effects play a crucial role for the determination of the adsorption barrier in the O2/Al system but their determination is hampered by serious technical problems that are discussed in detail.