Sokolovski D, De Fazio D, Cavalli S, Aquilanti V
School of Mathematics and Physics, Queen's University of Belfast, UKBT7 1NN.
Phys Chem Chem Phys. 2007 Nov 14;9(42):5664-71. doi: 10.1039/b709427b. Epub 2007 Sep 13.
We present a semiclassical complex angular momentum (CAM) analysis of the forward scattering peak which occurs at a translational collision energy around 32 meV in the quantum mechanical calculations for the F + H(2)(v = 0, j = 0) --> HF(v' = 2, j' = 0) + H reaction on the Stark-Werner potential energy surface. The semiclassical CAM theory is modified to cover the forward and backward scattering angles. The peak is shown to result from constructive/destructive interference of the two Regge states associated with two resonances, one in the transition state region and the other in the exit channel van der Waals well. In addition, we demonstrate that the oscillations in the energy dependence of the backward differential cross section are caused by the interference between the direct backward scattering and the decay of the two resonance complexes returning to the backward direction after one full rotation.
我们对在斯塔克 - 维尔纳势能面上F + H₂(v = 0, j = 0) → HF(v' = 2, j' = 0) + H反应的量子力学计算中,在约32毫电子伏特的平移碰撞能量处出现的前向散射峰进行了半经典复角动量(CAM)分析。对半经典CAM理论进行了修正,以涵盖前向和后向散射角。结果表明,该峰是由与两个共振相关的两个雷杰态的相长/相消干涉产生的,一个共振在过渡态区域,另一个在出射通道范德瓦尔斯阱中。此外,我们证明了后向微分截面能量依赖性中的振荡是由直接后向散射与两个共振复合体在完整旋转一周后返回后向方向的衰变之间的干涉引起的。