The role of depth and flatness of a potential energy surface in chemical reaction dynamics

DOI10.1134/S1560354720050044zbMATH Open1465.37070arXiv2003.14163MaRDI QIDQ2220892FDOQ2220892

Authors: Wenyang Lyu, Shibabrat Naik, Stephen Wiggins 

Publication date: 25 January 2021

Published in: Regular and Chaotic Dynamics (Search for Journal in Brave)

Abstract: In this study, we analyze how changes in the geometry of a potential energy surface in terms of depth and flatness can affect the reaction dynamics. We formulate depth and flatness in the context of one and two degree-of-freedom (DOF) Hamiltonian normal form for the saddle-node bifurcation and quantify their influence on chemical reaction dynamics. In a recent work, Garc'ia-Garrido, Naik, and Wiggins illustrated how changing the well-depth of a potential energy surface (PES) can lead to a saddle-node bifurcation. They have shown how the geometry of cylindrical manifolds associated with the rank-1 saddle changes en route to the saddle-node bifurcation. Using the formulation presented here, we show how changes in the parameters of the potential energy control the depth and flatness and show their role in the quantitative measures of a chemical reaction. We quantify this role of the depth and flatness by calculating the ratio of the bottleneck-width and well-width, reaction probability (also known as transition fraction or population fraction), gap time (or first passage time) distribution, and directional flux through the dividing surface (DS) for small to high values of total energy. The results obtained for these quantitative measures are in agreement with the qualitative understanding of the reaction dynamics.

Full work available at URL: https://arxiv.org/abs/2003.14163

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zbMATH Keywords

Monte Carlo simulationchemical reactiondepthflatnesspotential energy surfacesaddle-node bifurcationBorn-Oppenheimer approximationnormally hyperbolic invariant manifoldHamiltonian vector fielddegree of freedomreaction probabilityunstable periodic orbitgap timerecurrence theoremdividing surfacebottleneck widthdirectional flux

Mathematics Subject Classification ID

Bifurcation problems for finite-dimensional Hamiltonian and Lagrangian systems (37J20) Chemically reacting flows (80A32) Normal forms for dynamical systems (37G05) Classical flows, reactions, etc. in chemistry (92E20) Relations of finite-dimensional Hamiltonian and Lagrangian systems with topology, geometry and differential geometry (symplectic geometry, Poisson geometry, etc.) (37J39) Applications of differential geometry to chemistry (53Z15)

Cites Work

• Geometry of escaping dynamics in nonlinear ship motion
• The geometry of reaction dynamics
• Direct construction of a dividing surface of minimal flux for multi-degree-of-freedom systems that cannot be recrossed
• A formula to compute the microcanonical volume of reactive initial conditions in transition state theory
• The role of normally hyperbolic invariant manifolds (NHIMS) in the context of the phase space setting for chemical reaction dynamics
• Tilting and squeezing: phase space geometry of Hamiltonian saddle-node bifurcation and its influence on chemical reaction dynamics

Cited In (6)

• Can we understand the branching of reaction valleys for more than two degrees of freedom?
• The influence of a parameter that controls the asymmetry of a potential energy surface with an entrance channel and two potential wells
• Hamiltonian pitchfork bifurcation in transition across index-1 saddles
• The nature of reactive and non-reactive trajectories for a three dimensional Caldera potential energy surface
• Deep Potential: A General Representation of a Many-Body Potential Energy Surface
• Transition criteria and phase space structures in a three degree of freedom system with dissipation

Uses Software

• UPOsHam

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