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Correlated Molecular Orbital Theory Study of the Al + CO2 Reaction
The Journal of Physical Chemistry A ( IF 2.9 ) Pub Date : 2018-01-10 00:00:00 , DOI: 10.1021/acs.jpca.7b11443
Rezvan Chitsazi 1 , Jeffrey D. Veals 2 , Yi Shi 1 , Tommy Sewell 1
Affiliation  

Density functional theory (DFT) and correlated molecular orbital electronic structure calculations were used to study the Al + CO2 → AlO + CO reaction on the electronic ground-state potential-energy surface (PES). Geometries were optimized using DFT (M11/jun-cc-pV(Q+d)Z) and more accurate energies were obtained using the composite Weizmann-1 theory with Brueckner doubles (W1BD). The results comprise the most complete, most systematic characterization of the Al + CO2 reaction surface to date and are based on consistent application of high-level methods for all stationary points identified. The pathways from Al + CO2 to AlO + CO on the electronic ground-state PES all involve formation of one or more stable AlCO2 complexes denoted η-AlCO2, trans-AlCO2, and C2v-AlCO2, among which η-AlCO2 and C2v-AlCO2 are the least and most stable, respectively. We report a new minimum-energy pathway for the overall reaction, namely formation of η-AlCO2 from reactants and dissociation of that same complex to products via a bond-insertion reaction that passes through a fourth (weakly metastable) AlCO2 complex denoted cis-OAlCO. Natural Bond Orbital analysis was applied to study trends in charge distribution and the degree of charge transfer in key structures along the minimum-energy pathway. The process of aluminum insertion into CO2 is discussed in the context of analogous processes for boron and first-row transition metals.

中文翻译:

Al + CO 2反应的相关分子轨道理论研究

利用密度泛函理论(DFT)和相关的分子轨道电子结构计算研究了电子基态势能表面(PES)上的Al + CO 2 →AlO + CO反应。使用DFT(M11 / jun-cc-pV(Q + d)Z)优化几何形状,并使用带有Brueckner double的复合Weizmann-1理论(W1BD)获得更精确的能量。结果包括迄今为止对Al + CO 2反应表面的最完整,最系统的表征,并且基于对所有确定的固定点均采用高级方法的一致应用。电子基态PES上从Al + CO 2到AlO + CO的路径均涉及一种或多种稳定的AlCO 2络合物的形成,表示为η- ALCO 2反式-AlCO 2,和c ^ 2 v -AlCO 2,其中η- ALCO 2c ^ 2 v -AlCO 2分别是至少和最稳定的。我们报告了整个反应的新的最小能量途径,即从反应物形成η- AlCO 2,并通过键插入反应使相同的配合物解离成产物,该键插入反应通过称为顺式的第四个(弱亚稳)AlCO 2配合-OALCO。使用自然键轨道分析来研究沿最小能量途径的关键结构中电荷分布和电荷转移程度的趋势。在用于硼和第一行过渡金属的类似过程的背景下讨论了将铝插入CO 2的过程。
更新日期:2018-01-10
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