Global reaction route mapping on potential energy surfaces of formaldehyde, formic acid, and their metal-substituted analogues
Global reaction route mapping on potential energy surfaces of formaldehyde, formic acid, and their metal-substituted analogues
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DOI：
10.1021/jp061149l
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发表时间：
2006-07-20
影响因子：
2.9
通讯作者：
Maeda, Satoshi
中科院分区：
文献类型：
--
作者：
Ohno, Koichi;Maeda, Satoshi
对MCHO（M = H，Li，Na，Al，Cu）和HCO_2M（M = H，Li）体系的平衡结构、过渡结构及其相互关系在势能面上进行了全局反应路线图绘制.基于定标超球搜索方法的一个接一个的技术已经成功地应用于探索未知的化学结构，过渡结构，和有机金属体系的反应途径。金属取代后，稳定结构、反应途径和过渡结构的相对高度都发生了很大的变化，尽管类似物之间的一些特征是相似的。发现Al和Cu原子表现出很强的剪切CO双键的行为。CO插入Li-H键和Li-CH 3键的能量分布非常相似，特别是在Li原子不直接与甲基连接的结构周围，这表明烷基取代对反应路线拓扑结构的影响很小。
Global reaction route mapping of equilibrium structures, transition structures, and their connections on potential energy surface ( PES) has been done for MCHO (M = H, Li, Na, Al, Cu) and HCO2M (M = H, Li). A one-after-another technique based on the scaled hypersphere search method has been successfully applied to exploring unknown chemical structures, transition structures, and reaction pathways for organometallic systems. Upon metal substitution, considerable changes of stable structures, reaction pathways, and relative heights of transition structures have been discovered, though some features are similar among the analogues. Al and Cu atoms were found to behave as very strong scissors to cut the CO double bond in MCHO. Energy profiles of the CO insertion into Li-H and Li-CH3 bonds were found to be very similar, especially around the structures where the Li atom is not directly connected with the methyl group, which indicates little effects of alkyl substitution on the reaction route topology.