Ab initio Prediction of the Structures and Stabilities of the Hyperaluminum Molecules: Al3O and Square-Planar Al4O.
Ab initio Prediction of the Structures and Stabilities of the Hyperaluminum Molecules: Al3O and Square-Planar Al4O.
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DOI：
10.1002/chin.199210001
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发表时间：
1992-03
期刊：
影响因子：
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通讯作者：
A. Boldyrev;P. Schleyer
中科院分区：
文献类型：
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作者：
A. Boldyrev;P. Schleyer
超金属化的概念，其特征在于具有前所未有的化学计量比的分子，被扩展到铝-氧组合，A130和A140。在HF/6- 31 G * 和MP2（full）/6 - 31 G * 下计算了它们的平衡几何构型和基频，以及孤立参比物种AlO，Al 2，Al 2+，A120，A130+，A130，Al 3+，Al 42+和A140的平衡几何构型和基频。对可能的结构和电子状态进行了广泛的搜索。全局最小值是：线性A120（i）n *，i+），平面A130+（2A）3，“A，”），平面A130（Y（2A）和T（2B）2形式具有几乎相同的能量），四面体A142+（“A，”），和平面A140（Dik，* Alg）。所有这些物种在所有可能的分解途径方面都非常稳定（Al 42+除外）。代表性的解离能（在PMP 4SDTQ/6- 311 + G*//MP2（全）/6- 31 G *+ ZPE下以kcal/mol计）为：（34.1）; A130，转化为A120+ Al（19.9）; A140，转化为A130+ Al（45.5）或转化为A120+ Al 2（37.1）。尽管铝氧吸引力在很大程度上
The concept of hypermetalation, characterized by molecules with unprecedented stoichiometries, is extended to the aluminum-oxygen combinations, A130and A140. Their equilibrium geometries and fundamental frequencies, as well as those of the isolated reference species AlO, Al2, Al2+, A120, A130+, A130, Al3+, Al42+, and A140, were calculated at HF/6-31G* and at various correlated levels, eg, MP2 (full)/6-31G*. Extensive searches of possible structures and electronic states were carried out. The global minima are: linear A120 (/)„*,‘.+), planar A130+() 3,'A,'), planar A130 (the Y (2A]) andT (2B2) forms have nearly the same energy), tetrahedral Al42+('A,), and planarAI40 (Dik,* Alg). All these species are very stable (with the exception of Al42+) with regard to all possible decomposition pathways. Representative dissociation energies (in kcal/mol at PMP4SDTQ/6-31 l+ G*//MP2 (full)/6-31G*+ ZPE) are: A130+, into A120+ A!+(34.1); A130, into A120+ Al (19.9); A140, into A130+ A1 (45.5) or into A120+ Al2 (37.1). Although the aluminum-oxygen attraction is largely