Normally Hyperbolic Invariant Manifold Research Articles

3D Generating Surfaces in Hamiltonian Systems with Three Degrees of Freedom – II

Our paper is a continuation of a previous work referenced as [Katsanikas & Wiggins, 2024b ]. In this new paper, we present a second method for computing three-dimensional generating surfaces in Hamiltonian systems with three degrees of freedom. These 3D generating surfaces are distinct from the Normally Hyperbolic Invariant Manifold (NHIM) and have the unique property of producing dividing surfaces with no-recrossing characteristics, as explained in our previous work [Katsanikas & Wiggins, 2024b ]. This second method for computing 3D generating surfaces is valuable, especially in cases where the first method is unable to achieve the desired results. This research aims to provide alternative techniques and solutions for addressing specific challenges in Hamiltonian systems with three degrees of freedom and improving the accuracy and reliability of generating surfaces. This research may find applications in the broader field of dynamical systems and attract the attention of researchers and scholars interested in these areas.

Optimal Stabilization of Periodic Orbits

In this contribution the optimal stabilization problem of periodic orbits is studied in a symplectic geometry setting. For this, the stable manifold theory for the point stabilization case is generalized to the case of periodic orbit stabilization. Sufficient conditions for the existence of a normally hyperbolic invariant manifold (NHIM) of the Hamiltonian system are derived. It is shown that the optimal control problem has a solution if the related periodic Riccati equation has a unique periodic solution. For the analysis of the stable and unstable manifold a coordinate transformation is used which is moving along the orbit. As an example, an optimal control problem is considered for a spring-mass oscillator system, which should be stabilized at a certain energy level.

A deep dive into the $$2g+h$$ resonance: separatrices, manifolds and phase space structure of navigation satellites

Despite extended past studies, several questions regarding the resonant structure of the medium-Earth orbit (MEO) region remain hitherto unanswered. This work describes in depth the effects of the $2g+h$ lunisolar resonance. In particular, (i) we compute the correct forms of the separatrices of the resonance in the inclination-eccentricity space for fixed semi-major axis. This allows to compute the change in the width of the $2g+h$ resonance as the altitude increases. (ii) We discuss the crucial role played by the value of the inclination of the Laplace plane, $i_{L}$. Since $i_L$ is comparable to the resonance's separatrix width, the parametrization of all resonance bifurcations has to be done in terms of the proper inclination $i_{p}$, instead of the mean one. (iii) The subset of circular orbits constitutes an invariant subspace embedded in the full phase space, the center manifold $\mathcal{C}$. Using $i_p$ as a label, we compute its range of values for which $\mathcal{C}$ becomes a normally hyperbolic invariant manifold (NHIM). The structure of invariant tori in $\mathcal{C}$ allows to explain the role of the initial phase $h$ noticed in several works. (iv) Through Fast Lyapunov Indicator (FLI) cartography, we portray the stable and unstable manifolds of the NHIM as the altitude increases. Manifold oscillations dominate in phase space between $a=24,000$ km and $a=30,000$ km as a result of the sweeping of the $2g+h$ resonance by the $h-\Omega_{\rm{Moon}}$ and $2h-\Omega_{\rm{Moon}}$ resonances. The noticeable effects of the latter are explained as a consequence of the relative inclination of the Moon's orbit with respect to the ecliptic. The role of the phases $(h,\Omega_{\rm{Moon}})$ in the structures observed in the FLI maps is also clarified. Finally,(v) we discuss how the understanding of the manifold dynamics could inspire end-of-life disposal strategies.

Phase space geometry of isolated to condensed chemical reactions.

The complexity of gas and condensed phase chemical reactions has generally been uncovered either approximately through transition state theories or exactly through (analytic or computational) integration of trajectories. These approaches can be improved by recognizing that the dynamics and associated geometric structures exist in phase space, ensuring that the propagator is symplectic as in velocity-Verlet integrators and by extending the space of dividing surfaces to optimize the rate variationally, respectively. The dividing surface can be analytically or variationally optimized in phase space, not just over configuration space, to obtain more accurate rates. Thus, a phase space perspective is of primary importance in creating a deeper understanding of the geometric structure of chemical reactions. A key contribution from dynamical systems theory is the generalization of the transition state (TS) in terms of the normally hyperbolic invariant manifold (NHIM) whose geometric phase-space structure persists under perturbation. The NHIM can be regarded as an anchor of a dividing surface in phase space and it gives rise to an exact non-recrossing TS theory rate in reactions that are dominated by a single bottleneck. Here, we review recent advances of phase space geometrical structures of particular relevance to chemical reactions in the condensed phase. We also provide conjectures on the promise of these techniques toward the designand control of chemical reactions.

The Generalization of the Periodic Orbit Dividing Surface for Hamiltonian Systems with Three or More Degrees of Freedom – II

We develop a method for the construction of a dividing surface using periodic orbits in Hamiltonian systems with three or more degrees-of-freedom that is an alternative to the method presented in [ Katsanikas & Wiggins, 2021 ]. Similar to that method, for an [Formula: see text] degrees-of-freedom Hamiltonian system, we extend a one-dimensional object (the periodic orbit) to a [Formula: see text] dimensional geometrical object in the energy surface of a [Formula: see text] dimensional space that has the desired properties for a dividing surface. The advantage of this new method is that it avoids the computation of the normally hyperbolic invariant manifold (NHIM) (as the first method did) and it is easier to numerically implement than the first method of constructing periodic orbit dividing surfaces. Moreover, this method has less strict required conditions than the first method for constructing periodic orbit dividing surfaces. We apply the new method to a benchmark example of a Hamiltonian system with three degrees-of-freedom for which we are able to investigate the structure of the dividing surface in detail. We also compare the periodic orbit dividing surfaces constructed in this way with the dividing surfaces that are constructed starting with a NHIM. We show that these periodic orbit dividing surfaces are subsets of the dividing surfaces that are constructed from the NHIM.

Controlling reaction dynamics in chemical model systems through external driving

The rate of a chemical reaction can often be determined by the properties of a rank-1 saddle and the associated transition state separating reactants and products. We have found evidence that such rates can be controlled and even enhanced by external driving in at least one such system. Specifically, we analyze a reactive model in two degrees of freedom that has been used earlier to describe driven chemical reactions. Therein, changes in the external driving can lead to a local maximum of the decay rate constant or even to bifurcations of periodic trajectories on the normally hyperbolic invariant manifold (NHIM) corresponding to the transition state. Inspired by these bifurcations, we show that in this case, the dynamics on the NHIM can be connected to the geometry of reactive trajectories and to reaction probabilities of Maxwell–Boltzmann distributed reactant ensembles.

Thermal decay rates of an activated complex in a driven model chemical reaction.

Recent work has shown that in a nonthermal, multidimensional system, the trajectories in the activated complex possess different instantaneous and time-averaged reactant decay rates. Under dissipative dynamics, it is known that these trajectories, which are bound on the normally hyperbolic invariant manifold (NHIM), converge to a single trajectory over time. By subjecting these dissipative systems to thermal noise, we find fluctuations in the saddle-bound trajectories and their instantaneous decay rates. Averaging over these instantaneous rates results in the decay rate of the activated complex in a thermal system. We find that the temperature dependence of the activated complex decay in a thermal system can be linked to the distribution of the phase space resolved decay rates on the NHIM in the nondissipative case. By adjusting the external driving of the reaction, we show that it is possible to influence how the decay rate of the activated complex changes with rising temperature.

Dynamics and Bifurcations on the Normally Hyperbolic Invariant Manifold of a Periodically Driven System with Rank-1 Saddle

In chemical reactions, trajectories typically turn from reactants to products when crossing a dividing surface close to the normally hyperbolic invariant manifold (NHIM) given by the intersection of the stable and unstable manifolds of a rank-1 saddle. Trajectories started exactly on the NHIM in principle never leave this manifold when propagated forward or backward in time. This still holds for driven systems when the NHIM itself becomes time dependent. We investigate the dynamics on the NHIM for a periodically driven model system with two degrees of freedom by numerically stabilizing the motion. Using Poincar\'e surfaces of section we demonstrate the occurrence of structural changes of the dynamics, \emph{viz.}, bifurcations of periodic transition state (TS) trajectories when changing the amplitude and frequency of the external driving. In particular, periodic TS trajectories with the same period as the external driving but significantly different parameters---such as mean energy---compared to the ordinary TS trajectory can be created in a saddle-node bifurcation.

Tilting and Squeezing: Phase Space Geometry of Hamiltonian Saddle-Node Bifurcation and its Influence on Chemical Reaction Dynamics

In this article, we present the influence of a Hamiltonian saddle-node bifurcation on the high-dimensional phase space structures that mediate reaction dynamics. To achieve this goal, we identify the phase space invariant manifolds using Lagrangian descriptors, which is a trajectory-based diagnostic suitable for the construction of a complete “phase space tomography” by means of analyzing dynamics on low-dimensional slices. First, we build a Hamiltonian system with one degree-of-freedom (DoF) that models reaction, and study the effect of adding a parameter to the potential energy function that controls the depth of the well. Then, we extend this framework to a saddle-node bifurcation for a two DoF Hamiltonian, constructed by coupling a harmonic oscillator, i.e. a bath mode, to the other reactive DoF in the system. For this problem, we describe the phase space structures associated with the rank-1 saddle equilibrium point in the bottleneck region, which is a Normally Hyperbolic Invariant Manifold (NHIM) and its stable and unstable manifolds. Finally, we address the qualitative changes in the reaction dynamics of the Hamiltonian system due to changes in the well depth of the potential energy surface that gives rise to the saddle-node bifurcation.

Neural network approach for the dynamics on the normally hyperbolic invariant manifold of periodically driven systems.

Chemical reactions in multidimensional systems are often described by a rank-1 saddle, whose stable and unstable manifolds intersect in the normally hyperbolic invariant manifold (NHIM). Trajectories started on the NHIM in principle never leave this manifold when propagated forward or backward in time. However, the numerical investigation of the dynamics on the NHIM is difficult because of the instability of the motion. We apply a neural network to describe time-dependent NHIMs and use this network to stabilize the motion on the NHIM for a periodically driven model system with two degrees of freedom. The method allows us to analyze the dynamics on the NHIM via Poincaré surfaces of section (PSOS) and to determine the transition-state (TS) trajectory as a periodic orbit with the same periodicity as the driving saddle, viz. a fixed point of the PSOS surrounded by near-integrable tori. Based on transition state theory and a Floquet analysis of a periodic TS trajectory we compute the rate constant of the reaction with significantly reduced numerical effort compared to the propagation of a large trajectory ensemble.

Phase-space resolved rates in driven multidimensional chemical reactions

Chemical reactions in multidimensional driven systems are typically described by a time-dependent rank-1 saddle associated with one reaction and several orthogonal coordinates (including the solvent bath). To investigate reactions in such systems, we develop a fast and robust method-viz., local manifold analysis (LMA)-for computing the instantaneous decay rate of reactants. Specifically, it computes the instantaneous decay rates along saddle-bound trajectories near the activated complex by exploiting local properties of the stable and unstable manifold associated with the normally hyperbolic invariant manifold (NHIM). The LMA method offers substantial reduction in numerical effort and increased reliability in comparison with direct ensemble integration. It provides an instantaneous flux that can be assigned to every point on the NHIM and which is associated with a trajectory-regardless of whether it is periodic, quasiperiodic, or chaotic-that is bound on the NHIM. The time average of these fluxes in the driven system corresponds to the average rate through a given local section containing the corresponding point on the NHIM. We find good agreement between the results of the LMA and direct ensemble integration obtained using numerically constructed, recrossing-free dividing surfaces.

Chaotic transport of navigation satellites.

Navigation satellites are known from numerical studies to reside in a dynamically sensitive environment, which may be of profound importance for their long-term sustainability. We derive the fundamental Hamiltonian of Global Navigation Satellite System dynamics and show analytically that near-circular trajectories lie in the neighborhood of a Normally Hyperbolic Invariant Manifold (NHIM), which is the primary source of hyperbolicity. Quasicircular orbits escape through chaotic transport, regulated by NHIM's stable and unstable manifolds, following a power-law escape time distribution P(t)∼t-α, with α∼0.8-1.5. Our study is highly relevant for the design of satellite disposal trajectories, using manifold dynamics.

Invariant Manifolds and Rate Constants in Driven Chemical Reactions.

Reaction rates of chemical reactions under nonequilibrium conditions can be determined through the construction of the normally hyperbolic invariant manifold (NHIM) [and moving dividing surface (DS)] associated with the transition state trajectory. Here, we extend our recent methods by constructing points on the NHIM accurately even for multidimensional cases. We also advance the implementation of machine learning approaches to construct smooth versions of the NHIM from a known high-accuracy set of its points. That is, we expand on our earlier use of neural nets and introduce the use of Gaussian process regression for the determination of the NHIM. Finally, we compare and contrast all of these methods for a challenging two-dimensional model barrier case so as to illustrate their accuracy and general applicability.

Global linearization and fiber bundle structure of invariant manifolds

We study global properties of the global (center-)stable manifold of a normally attracting invariant manifold (NAIM), the special case of a normally hyperbolic invariant manifold (NHIM) with empty unstable bundle. We restrict our attention to continuous-time dynamical systems, or flows. We show that the global stable foliation of a NAIM has the structure of a topological disk bundle, and that similar statements hold for inflowing NAIMs and for general compact NHIMs. Furthermore, the global stable foliation has a Ck disk bundle structure if the local stable foliation is assumed Ck. We then show that the dynamics restricted to the stable manifold of a compact inflowing NAIM are globally topologically conjugate to the linearized transverse dynamics at the NAIM. Moreover, we give conditions ensuring the existence of a global Ck linearizing conjugacy. We also prove a Ck global linearization result for inflowing NAIMs; we believe that even the local version of this result is new, and may be useful in applications to slow-fast systems. We illustrate the theory by giving applications to geometric singular perturbation theory in the case of an attracting critical manifold: we show that the domain of the Fenichel normal form can be extended to the entire global stable manifold, and under additional nonresonance assumptions we derive a smooth global linear normal form.

The role of normally hyperbolic invariant manifolds (NHIMS) in the context of the phase space setting for chemical reaction dynamics

In this paper we give an introduction to the notion of a normally hyperbolic invariant manifold (NHIM) and its role in chemical reaction dynamics.We do this by considering simple examples for one-, two-, and three-degree-of-freedom systems where explicit calculations can be carried out for all of the relevant geometrical structures and their properties can be explicitly understood. We specifically emphasize the notion of a NHIM as a “phase space concept”. In particular, we make the observation that the (phase space) NHIM plays the role of “carrying” the (configuration space) properties of a saddle point of the potential energy surface into phase space. We also consider an explicit example of a 2-degree-of-freedom system where a “global” dividing surface can be constructed using two index one saddles and one index two saddle. Such a dividing surface has arisen in several recent applications and, therefore, such a construction may be of wider interest.

Phase-space geometry and reaction dynamics near index 2 saddles

We study the phase-space geometry associated with index 2 saddles of a potential energy surface and its influence on reaction dynamics for n degree-of-freedom (DoF) Hamiltonian systems. In recent years, similar studies have been carried out for index 1 saddles of potential energy surfaces, and the phase-space geometry associated with classical transition state theory has been elucidated. In this case, the existence of a normally hyperbolic invariant manifold (NHIM) of saddle stability type has been shown, where the NHIM serves as the ‘anchor’ for the construction of dividing surfaces having the no-recrossing property and minimal flux. For the index 1 saddle case, the stable and unstable manifolds of the NHIM are co-dimension 1 in the energy surface and have the structure of spherical cylinders, and thus act as the conduits for reacting trajectories in phase space. The situation for index 2 saddles is quite different, and their relevance for reaction dynamics has not previously been fully recognized. We show that NHIMs with their stable and unstable manifolds still exist, but that these manifolds by themselves lack sufficient dimension to act as barriers in the energy surface in order to constrain reactions. Rather, in the index 2 case there are different types of invariant manifolds, containing the NHIM and its stable and unstable manifolds, that act as co-dimension 1 barriers in the energy surface. These barriers divide the energy surface in the vicinity of the index 2 saddle into regions of qualitatively different trajectories exhibiting a wider variety of dynamical behavior than for the case of index 1 saddles. In particular, we can identify a class of trajectories, which we refer to as ‘roaming trajectories’, which are not associated with reaction along the classical minimum energy path (MEP). We illustrate the significance of our analysis of the index 2 saddle for reaction dynamics with two examples. The first involves isomerization on a potential energy surface with multiple (four) symmetry equivalent minima; the dynamics in the vicinity of the saddle enables a rigorous distinction to be made between stepwise (sequential) and concerted (hilltop crossing) isomerization pathways. The second example involves two potential minima connected by two distinct transition states associated with conventional index 1 saddles, and an index 2 saddle that sits between the two index 1 saddles. For the case of non-equivalent index 1 saddles, our analysis suggests a rigorous dynamical definition of ‘non-MEP’ or ‘roaming’ reactive events.

Dynamical foundation and limitations of statistical reaction theory

We study the foundation and limitations of the statistical reaction theory. In particular, we focus our attention to the question of whether the rate constant can be defined for nonergodic systems. Based on the analysis of the Arnold web in the reactant well, we show that the survival probability exhibits two types of behavior: one where it depends on the residential time as the power-law decay and the other where it decays exponentially. The power-law decay casts a doubt on definability of the rate constant for nonergodic systems. We indicate that existence of the two types of behavior comes from sub-diffusive motions in remote regions from resonance overlap. Moreover, based on analysis of nonstationary features of trajectories, we can understand how the normally hyperbolic invariant manifold (NHIM) is connected with the Arnold web. We propose that the following two features play a key role in understanding the reactions where ergodicity is broken, i.e., whether the Arnold web is nonuniform and how the NHIM is connected with the Arnold web.

Phase space conduits for reaction in multidimensional systems: HCN isomerization in three dimensions.

The three-dimensional hydrogen cyanide/isocyanide isomerization problem is taken as an example to present a general theory for computing the phase space structures which govern classical reaction dynamics in systems with an arbitrary (finite) number of degrees of freedom. The theory, which is algorithmic in nature, comprises the construction of a dividing surface of minimal flux which is locally a "surface of no return." The theory also allows for the computation of the global phase space transition pathways that trajectories must follow in order to react. The latter are enclosed by the stable and unstable manifolds of a so-called normally hyperbolic invariant manifold (NHIM). A detailed description of the geometrical structures and the resulting constraints on reaction dynamics is given, with particular emphasis on the three degrees of freedom case. A procedure is given which uses these structures to compute orbits homoclinic to, and heteroclinic between, NHIMs. The role of homoclinic and heteroclinic orbits in global recrossings of dividing surfaces and transport in complex systems is explained. The complete description provided here is inherently one within phase space; it cannot be inferred from a configuration space picture. A complexification of the classical phase space structures to incorporate quantum effects is also discussed. The results presented here call into question certain assumptions routinely made on the global dynamics; this paper provides methods that enable one to understand and quantify the phase space dynamics of reactions without making such assumptions.

A computational procedure to detect a new type of high-dimensional chaotic saddle and its application to the 3D Hill's problem

A computational procedure that allows the detection of a new type of high-dimensional chaotic saddle in Hamiltonian systems with three degrees of freedom is presented. The chaotic saddle is associated with a so-called normally hyperbolic invariant manifold (NHIM). The procedure allows to compute appropriate homoclinic orbits to the NHIM from which we can infer the existence a chaotic saddle. NHIMs control the phase space transport across an equilibrium point of saddle-centre-...-centre stability type, which is a fundamental mechanism for chemical reactions, capture and escape, scattering, and, more generally, ``transformation'' in many different areas of physics. Consequently, the presented methods and results are of broad interest. The procedure is illustrated for the spatial Hill's problem which is a well known model in celestial mechanics and which gained much interest e.g. in the study of the formation of binaries in the Kuiper belt.

The geometry of reaction dynamics

The geometrical structures which regulate transformations in dynamicalsystems with three or more degrees of freedom (DOFs) form the subject of thispaper. Our treatment focuses on the (2n-3)-dimensional normallyhyperbolic invariant manifold (NHIM) in nDOF systemsassociated with a centre×···×centre×saddle in the phase space flow in the(2n-1)-dimensional energy surface. The NHIM bounds a (2n-2)-dimensionalsurface, called a `transition state' (TS) in chemical reaction dynamics,which partitions the energy surface into volumes characterized as`before' and `after' the transformation. This surface is thelong-sought momentum-dependent TS beyond two DOFs. The (2n-2)-dimensional stable and unstable manifolds associatedwith the (2n-3)-dimensional NHIM are impenetrable barriers with thetopology of multidimensional spherical cylinders. The phase flowinterior to these spherical cylinders passes through the TS as the system undergoes its transformation. The phase flowexterior to these spherical cylinders is directed away from theTS and, consequently, will never undergo the transition.The explicit forms of these phase space barriers can be evaluated usingnormal form theory. Our treatment has the advantage of supplying apractical algorithm, and we demonstrate its use on a strongly couplednonlinear Hamiltonian, the hydrogen atom in crossed electric andmagnetic fields.