Atomic Alignment Effect in the Dissociative Energy Transfer Reactions of Metal Carbonyls [Fe (CO)5, Ni (CO)4] with Oriented Ar (3P2)
Atomic Alignment Effect in the Dissociative Energy Transfer Reactions of Metal Carbonyls [Fe (CO)5, Ni (CO)4] with Oriented Ar (3P2)
复制标题
金属羰基化合物 [Fe (CO)5, Ni (CO)4] 与取向 Ar (3P2) 解离能转移反应中的原子排列效应
DOI：
10.1021/jp206670w
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发表时间：
2011
期刊：
影响因子：
2.9
通讯作者：
Y. Matsuura
中科院分区：
文献类型：
--
作者：
H. Ohoyama;Y. Matsuura
研究了金属羰基(Fe（CO)5, Ni(CO)4）与取向Ar （3P2，MJ= 2）的离解能转移反应的原子排列效应。测量了受激金属产物（Fe*, Ni*）的发射强度作为碰撞框架中原子排列的函数。在两种反应体系中，Ar (3P2，MJ= 2)（2阶矩，a2）的原子轨道排列选择性相反；Fe(CO)5反应在Π构型（正a2）下有利，而Ni(CO)4反应在Σ构型（负a2）下有利。此外，仅在Ni(CO)4反应中发现了显著的自旋取向效应（4阶矩，a4）。结果表明，两种反应体系的原子排列效应存在本质差异；Fe(CO)5反应受Ar （3P2）半填满的3p原子轨道的构型控制（独立），而Ni(CO)4反应受Ar （3P2）的总角动量j（包括自旋）的构型控制（独立）。由于仅在Ni(CO)4反应中观察到依赖性的来源，因此提出了通过电子重排的两个电子交换过程之间的关联（和/或干扰）。
The atomic alignment effect has been studied for the dissociative energy transfer reaction of metal carbonyls (Fe(CO)5, Ni(CO)4) with the oriented Ar (3P2,MJ= 2). The emission intensity from the excited metal products (Fe*, Ni*) has been measured as a function of the atomic alignment in the collision frame. The selectivity of the atomic orbital alignment of Ar (3P2,MJ= 2) (rank 2 moment, a2) is found to be opposite for the two reaction systems; the Fe(CO)5reaction is favorable at the Π configuration (positive a2), while the Ni(CO)4reaction is favorable at the Σ configuration (negative a2). Moreover, a significant spin alignment effect (rank 4 moment, a4) is recognized only in the Ni(CO)4reaction. The atomic alignment effect turns out to be essentially different between the two reaction systems; the Fe(CO)5reaction is controlled by the configuration of the half-filled 3p atomic orbital of Ar (3P2) in the collision frame (Ldependence), whereas the Ni(CO)4reaction is controlled by the configuration of the total angular momentJ(including spin) of Ar (3P2) in the collision frame (Jdependence). As the origin ofJdependence observed only in the Ni(CO)4reaction, the correlation (and/or the interference) between two electron exchange processes via the electron rearrangements is proposed.