中央研究院 原子與分子科學研究所

Huilin Pan, Fengyan Wang, Gábor Czakó, and Kopin Liu*

Nature Chemistry, 9, 1175-1180 (2017).

The transition state, which gates and modulates the reactive flux, serves as the central concept in our understanding of activated reactions. The barrier height of the transition state can be estimated from the activation energy taken from thermal kinetics data or from the energetic threshold in the measured excitation function (the dependence of reaction cross sections on initial collision energies). However, another critical and equally important property, the angle-dependent barrier to reaction, has not yet been amenable to experimental determination until now. Here, using the benchmark reaction of Cl + CHD₃(v1 = 1) as an example, we show how to map this anisotropic property of the transition state as a function of collision energy from the preferred reactant bond alignment of the backward-scattered products ‒ the imprints of small impact-parameter collisions (left figure). The deduced bend potential at the transition state agrees with ab initio calculations (right figure). We expect that the method should be applicable to many other direct reactions with a collinear barrier.