Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
J Chem Phys. 2013 Dec 21;139(23):234308. doi: 10.1063/1.4844315.
The vector correlation between the alignment of reactant N2 (A (3)Σu(+)) and the alignment of product NO (A (2)Σ(+)) rotation has been studied in the energy transfer reaction of aligned N2 (A (3)Σu(+)) + NO (X (2)Π) → NO (A (2)Σ(+)) + N2 (X (1)Σg(+)) under the crossed beam condition at a collision energy of ~0.07 eV. NO (A (2)Σ(+)) emission in the two linear polarization directions (i.e., parallel and perpendicular with respect to the relative velocity vector v(R)) has been measured as a function of the alignment of N2 (A (3)Σu(+)) along its molecular axis in the collision frame. The degree of polarization of NO (A (2)Σ(+)) emission is found to depend on the alignment angle (θ(v(R))) of N2 (A (3)Σu(+)) in the collision frame. The shape of the steric opacity function at the two polarization conditions turns out to be extremely different from each other: The steric opacity function at the parallel polarization condition is more favorable for the oblique configuration of N2 (A (3)Σu(+)) at an alignment angle of θ(v(R)) ~ 45° as compared with that at the perpendicular polarization condition. The alignment of N2 (A (3)Σu(+)) is found to give a significant effect on the alignment of NO (A (2)Σ(+)) rotation in the collision frame: The N2 (A (3)Σu(+)) configuration at an oblique alignment angle θ(v(R)) ~ 45° leads to a parallel alignment of NO (A (2)Σ(+)) rotation (J-vector) with respect to v(R), while the axial and sideways configurations of N2 (A (3)Σu(+)) lead to a perpendicular alignment of NO (A (2)Σ(+)) rotation with respect to vR. These stereocorrelated alignments of the product rotation have a good correlation with the stereocorrelated reactivity observed in the multi-dimensional steric opacity function [H. Ohoyama and S. Maruyama, J. Chem. Phys. 137, 064311 (2012)].
在碰撞能约为 0.07eV 的交叉束条件下,研究了在 N2(A(3)Σu(+))取向和产物 NO(A(2)Σ(+))旋转取向之间的矢量相关性,能量转移反应 N2(A(3)Σu(+))+NO(X(2)Π)→NO(A(2)Σ(+))+N2(X(1)Σg(+))。已测量了在两个线性偏振方向(即相对于相对速度矢量 v(R)平行和垂直)上的 NO(A(2)Σ(+))发射的偏振度,作为碰撞框架中 N2(A(3)Σu(+))沿着其分子轴的取向的函数。NO(A(2)Σ(+))发射的偏振度被发现取决于碰撞框架中 N2(A(3)Σu(+))的取向角(θ(v(R)))。在两个偏振条件下的立体遮挡函数的形状彼此非常不同:与垂直偏振条件相比,在平行偏振条件下,N2(A(3)Σu(+))在取向角θ(v(R))45°时的立体遮挡函数更有利于倾斜配置。发现 N2(A(3)Σu(+))的取向对碰撞框架中 NO(A(2)Σ(+))旋转的取向有显著影响:在倾斜取向角θ(v(R))45°处的 N2(A(3)Σu(+))构型导致 NO(A(2)Σ(+))旋转(J-矢量)相对于 v(R)的平行取向,而 N2(A(3)Σu(+))的轴向和侧向构型导致 NO(A(2)Σ(+))旋转相对于 vR 的垂直取向。这些产物旋转的立体相关取向与在多维立体遮挡函数中观察到的立体相关反应性有很好的相关性[H.Ohoyama 和 S.Maruyama,J.Chem.Phys.137,064311(2012)]。