The phase space mechanism for selectivity in a symmetric potential energy surface with a post-transition-state bifurcation

  title={The phase space mechanism for selectivity in a symmetric potential energy surface with a post-transition-state bifurcation},
  author={Makrina Agaoglou and V. J. Garc{\'i}a-Garrido and Matthaios Katsanikas and Stephen Wiggins},
  journal={Chemical Physics Letters},

Figures and Tables from this paper

Phase space analysis of the dynamics on a potential energy surface with an entrance channel and two potential wells.

The analysis of the geometrical template of phase space structures that governs transport in a Hamiltonian system described by a potential energy surface with an entrance/exit channel and two wells separated by an index-1 saddle reveals that the stable and unstable manifolds of the two families of unstable periodic orbits (UPOs) are responsible for controlling access to the potential wells of the trajectories that enter the system through the entrance/ exit channel.

Phase space structure and escape time dynamics in a Van der Waals model for exothermic reactions.

Random Gaussian bumps have been added to the Van der Waals potential energy to simulate the short-range effects between the particles in the system to compare both variants of the model and explain their differences and similarities from a phase space perspective.

From Poincaré Maps to Lagrangian Descriptors: The Case of the Valley Ridge Inflection Point Potential

In this paper we compare the method of Lagrangian descriptors with the classical method of Poincaré maps for revealing the phase space structure of two-degree-of-freedom Hamiltonian systems. The

Revealing the phase space structure of Hamiltonian systems using the action

In this work, we analyse the properties of the Maupertuis’ action as a tool to reveal the phase space structure for Hamiltonian systems. We construct a scalar field with the action’s values along the

Bifurcation of Dividing Surfaces Constructed from Period-Doubling Bifurcations of Periodic Orbits in a Caldera Potential Energy Surface

In this work we analyze the bifurcation of dividing surfaces that occurs as a result of two period-doubling bifurcations in a 2D caldera-type potential. We study the structure, the range, the minimum

The Influence of a Parameter that Controls the Asymmetry of a Potential Energy Surface with an Entrance Channel and Two Potential Wells

In this paper we study an asymmetric valley-ridge inflection point (VRI) potential, whose energy surface (PES) features two sequential index-1 saddles (the upper and the lower), with one saddle

Reaction Space Projector (ReSPer) for Visualizing Dynamic Reaction Routes Based on Reduced-Dimension Space

To analyze chemical reaction dynamics based on a reaction path network, we have developed the “Reaction Space Projector” (ReSPer) method with the aid of the dimensionality reduction method. This

The Time Evolution of the Trajectories After the Selectivity in a Symmetric Potential Energy Surface with a Post-transition-state Bifurcation

Selectivity is an important phenomenon in chemical reaction dynamics. This can be quantified by the branching ratio of the trajectories that visit one or the other well to the total number of



Post-transition state bifurcations gain momentum – current state of the field

Abstract The existence of post-transition state bifurcations on potential energy surfaces for organic and biological reaction mechanisms has been known for decades, but recently, new reports of

Lagrangian descriptors of driven chemical reaction manifolds.

It is demonstrated that this so-called distinguished trajectory is exact for harmonic barriers in one dimension and this verification gives impetus to the application of Lagrangian descriptor-based methods in diverse classes of chemical reactions.

Transition state geometry of driven chemical reactions on time-dependent double-well potentials.

P perturbation theory or Lagrangian descriptors are used to obtain the transition state trajectory and the associated recrossing-free dividing surface and determine the exact reactant population decay and the corresponding rates to benchmark the PT and LD approaches.

Lagrangian Descriptors of Thermalized Transition States on Time-Varying Energy Surfaces.

The generality of the formalism suggests that the reactive flux over a time-varying barrier can be determined without ambiguity in chemical reactions and is applicable to any activated system subjected to arbitrary driving and thermal fluctuations.

Chemical dynamics between wells across a time-dependent barrier: Self-similarity in the Lagrangian descriptor and reactive basins.

This work illustrates this behavior for a time-dependent double-well potential revealing a self-similar structure of the Lagrangian descriptors, and demonstrates how the reflections and side-minima can be addressed by an appropriate modification of the LD associated with the direct rate across the barrier.

Bifurcations and transition states

Bifurcations of reaction channels are related to valley-ridge inflection points and it is examined what happens when these do not coincide with transition states. Under such conditions there result

Deconstructing field-induced ketene isomerization through Lagrangian descriptors.

The time-dependent geometrical separatrices governing state transitions in field-induced ketene isomerization are constructed using the method of Lagrangian descriptors. We obtain the stable and

Lagrangian descriptors: A method for revealing phase space structures of general time dependent dynamical systems

Nonstatistical dynamics on potentials exhibiting reaction path bifurcations and valley-ridge inflection points.

It is found that apparently minor variations in the potential lead to significant changes in the reaction dynamics, and when dissipative effects are incorporated, the product ratio depends in a complicated and non-monotonic fashion on the dissipation parameter.