Department of Chemistry, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan.
J Chem Phys. 2012 Aug 14;137(6):064311. doi: 10.1063/1.4739273.
Steric effect for the NO (A (2)Σ(+)) formation in the aligned N(2) (A (3)Σ(u)(+)) + oriented NO (X (2)Π, Ω = 1∕2) reaction has been observed as a function of the mutual orientational configurations between the two molecular reactants in the collision frame. Multidimensional molecular steric opacity function has been determined. A significant NO (X (2)Π) alignment dependence is recognized in contrast with little dependence on NO (X (2)Π) orientation. The NO alignment selectivity turns out to depend on the N(2) (A (3)Σ(u)(+)) alignment: The axial configuration of NO (X (2)Π) is favorable for the axial and sideways configurations of N(2) (A (3)Σ(u)(+)), while the sideways configuration of NO (X (2)Π) is favorable for the oblique configuration of N(2) (A (3)Σ(u)(+)) at an orientation angle of θ(v(R)) ∼ 45°. with respect to the relative velocity (v(R)).
在碰撞框架中,作为两个分子反应物之间相互取向构型的函数,观察到了用于 NO(A(2)Σ(+))形成的空间位阻效应,这是在对齐的 N2(A(3)Σ(u)(+))+定向 NO(X(2)Π,Ω=1∕2)反应中。已经确定了多维分子位阻不透明度函数。与对 NO(X(2)Π)取向的几乎没有依赖性相比,发现了明显的 NO(X(2)Π)取向依赖性。NO 取向选择性取决于 N2(A(3)Σ(u)(+))的取向:NO(X(2)Π)的轴向构型有利于 N2(A(3)Σ(u)(+))的轴向和侧向构型,而 NO(X(2)Π)的侧向构型有利于在相对于相对速度(v(R))的取向角θ(v(R))∼45°时,N2(A(3)Σ(u)(+))的斜向构型。