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

DOI10.1134/S1560354720050044MaRDI QIDQ2220892zbMATH OpenFDO

Authors Wenyang Lyu, Shibabrat Naik, Stephen Wiggins

Publication date 25 January 2021

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

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

zbMATH Keywords

Born-Oppenheimer approximationbottleneck widthchemical reactiondegree of freedomdepthdirectional fluxdividing surfaceflatnessgap timeHamiltonian vector fieldMonte Carlo simulationnormally hyperbolic invariant manifoldpotential energy surfacereaction probabilityrecurrence theoremsaddle-node bifurcationunstable periodic orbit

Mathematics Subject Classification ID

Normal forms for dynamical systems (37G05) Bifurcation problems for finite-dimensional Hamiltonian and Lagrangian systems (37J20) 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) Chemically reacting flows (80A32) Classical flows, reactions, etc. in chemistry (92E20)

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.

Review text

The study of some qualitative properties of chemical reactions is here carried out via Hamiltonian bifurcation theory, in the cases of one and two degrees of freedom. The focus is on the geometry of the potential energy surface which describes how the potential energy depends on the coordinates. The two quantities used for mirroring the geometry of the ``potential energy landscape are depth and flatness. The former is the difference in potential energy between the saddle and the evolving center point at the bottom of the well, the latter is given by the average of the gradient norm of the potential energy. From the chemical viewpoint, depth and flatness are expected to heavily influence the reaction behavior, and, to investigate this, the effect on four particular quantities is calculated. The first one of these is the ratio of the bottleneck width and the well width. In the case of one degree of freedom, e.g., with phase space coordinates \(x\) and \(p_x\), a given energy (i.e., a single value of the Hamiltonian) singles out a particular orbit which is symmetric w.r.t. the \(x\)-axis. It shows a ``bottleneck where \(\vert p_x \vert\) has a local minimum. The bottleneck width then is the difference between the two values of \(p_x\) at that minimum. The well width is the difference between the two values of \(p_x\), where \(\vert p_x \vert\) has a local maximum. The second quantity calculated is a certain reaction probability. The third one, the gap time, refers to crossing times w.r.t. the so-called dividing surface. The fourth and final one is the directional flux through the dividing surface in the case of two degrees of freedom.

Recommendations

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Cites work

• A formula to compute the microcanonical volume of reactive initial conditions in transition state theory
• Direct construction of a dividing surface of minimal flux for multi-degree-of-freedom systems that cannot be recrossed
• Geometry of escaping dynamics in nonlinear ship motion
• The geometry of reaction dynamics
• 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)

• The influence of a parameter that controls the asymmetry of a potential energy surface with an entrance channel and two potential wells
• The nature of reactive and non-reactive trajectories for a three dimensional Caldera potential energy surface
• Hamiltonian pitchfork bifurcation in transition across index-1 saddles
• Can we understand the branching of reaction valleys for more than two degrees of freedom?
• 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

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