Ohoyama H, Yasuda K, Kasai T
Department of Chemistry, Graduate School of Science, Osaka University Toyonaka, Osaka 560-0043, Japan.
J Phys Chem A. 2008 Oct 30;112(43):10716-20. doi: 10.1021/jp806745g. Epub 2008 Oct 7.
Steric effect for the formation of N 2 (B, (3)Pi u ) in the energy transfer reaction of Kr ( (3)P 2) + N 2 has been measured using an oriented Kr ( (3)P 2, M J = 2) beam at a collision energy of 0.07 eV. The N 2 (B, (3)Pi u ) emission intensity was measured as a function of the magnetic orientation field direction in the collision frame. A significant atomic alignment effect on the energy transfer probability was observed. This result was compared with that for the formation of N 2 (C, (3)Pi g ) in the Ar ( (3)P 2) + N 2 reaction. Despite the large difference on the energy transfer cross-section, the atomic alignment dependence for Kr ( (3)P 2) + N 2 is found to be analogous to that for Ar ( (3)P 2) + N 2. It is revealed that the configuration of inner 4p (3p) orbital in the collision frame gives an important role for the stereoselectivity on electron transfer process via the curve-crossing mechanism.
在0.07 eV的碰撞能量下，使用取向的Kr(³P₂, MJ = 2)束流测量了Kr(³P₂) + N₂能量转移反应中N₂(B, ³Πu)形成的立体效应。在碰撞坐标系中，测量了N₂(B, ³Πu)发射强度作为磁取向场方向的函数。观察到了对能量转移概率的显著原子排列效应。将该结果与Ar(³P₂) + N₂反应中N₂(C, ³Πg)形成的结果进行了比较。尽管能量转移截面存在很大差异，但发现Kr(³P₂) + N₂的原子排列依赖性与Ar(³P₂) + N₂的类似。结果表明，碰撞坐标系中内部4p(3p)轨道的构型对通过曲线交叉机制的电子转移过程的立体选择性起着重要作用。
