Dynamical matching in a three-dimensional Caldera potential-energy surface

In a previous paper, we used a recent extension of the periodic-orbit dividing surfaces method to distinguish the reactive and nonreactive parts in a three-dimensional (3D) Caldera potential-energy surface. Furthermore, we detected the phenomenon of dynamical matching in a 3D Caldera potential-energy surface. This happened for a specific value of the radius r of the periodic orbit dividing surfaces (r = 0.25). In this paper, we demonstrated that the chemical ratios of the number of reactive and nonreactive trajectories to the total number of trajectories converges for a range of the radius r of the periodic-orbit dividing surfaces. This is important not only for validating the previous paper and to confirm that the method can detect the phenomenon of dynamical matching independently of the chosen radius of the construction of the dividing surface but also for investigating the application of the method to other Hamiltonian models.

Automated summary

In this study, a recent extension of the periodic-orbit dividing surfaces method was used to distinguish reactive and nonreactive parts in a three-dimensional Caldera potential-energy surface. The phenomenon of dynamical matching was detected in this surface for a specific radius of the periodic orbit dividing surfaces. It was demonstrated that the chemical ratios of reactive and nonreactive trajectories converge for a range of the radius, which has implications for validating the previous study and exploring the method's applicability to other Hamiltonian models.