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Stephen Wiggins

Publications and source records attributed to Stephen Wiggins.

At least 73 records · Page 4Linked to original sources
arXiv2018

Influence of mass and potential energy surface geometry on roaming in Chesnavich's CH$_4^+$ model

Chesnavich's model Hamiltonian for the reaction CH$_4^+ \rightarrow$ CH$_3^+$ is known to exhibit a range of interesting dynamical phenomena including roaming. The model system consists of two parts: a rigid, symmetric top representing the CH$_3^+$ ion and a free H atom. We study roaming in this model with focus on the evolution of geometrical features of the invariant manifolds in phase space that govern roaming under variations of the mass of the free atom m and a parameter a that couples radial and angular motion. In addition, we establish an upper bound on the prominence of roaming in Chesnavich's model. The bound highlights the intricacy of roaming as a type of dynamics on the verge between isomerisation and nonreactivity as it relies on generous access to the potential wells to allow reactions as well as a prominent area of high potential that aids sufficient transfer of energy between the degrees of freedom to prevent isomerisation.

math.DS↗
arXiv2018

Phase Space Structure and Transport in a Caldera Potential Energy Surface

We study phase space transport in a 2D caldera potential energy surface (PES) using techniques from nonlinear dynamics. The caldera PES is characterized by a flat region or shallow minimum at its center surrounded by potential walls and multiple symmetry related index one saddle points that allow entrance and exit from this intermediate region.We have discovered four qualitatively distinct cases of the structure of the phase space that govern phase space transport. These cases are categorized according to the total energy and the stability of the periodic orbits associated with the family of the central minimum, the bifurcations of the same family, and the energetic accessibility of the index one saddles. In each case we have computed the invariant manifolds of the unstable periodic orbits of the central region of the potential and the invariant manifolds of the unstable periodic orbits of the families of periodic orbits associated with the index one saddles. We have found that there are three distinct mechanisms determined by the invariant manifold structure of the unstable periodic orbits govern the phase space transport. The first mechanism explains the nature of the entrance of the trajectories from the region of the low energy saddles into the caldera and how they may become trapped in the central region of the potential. The second mechanism describes the trapping of the trajectories that begin from the central region of the caldera, their transport to the regions of the saddles, and the nature of their exit from the caldera. The third mechanism describes the phase space geometry responsible for the dynamical matching of trajectories originally proposed by Carpenter and described in Collins et al. (2014) for the two dimensional caldera PES that we consider.

nlin.CD↗
arXiv2017

High Dimensional Cluster Analysis Using Path Lengths

A hierarchical scheme for clustering data is presented which applies to spaces with a high number of dimension ($N_{_{D}}>3$). The data set is first reduced to a smaller set of partitions (multi-dimensional bins). Multiple clustering techniques are used, including spectral clustering, however, new techniques are also introduced based on the path length between partitions that are connected to one another. A Line-Of-Sight algorithm is also developed for clustering. A test bank of 12 data sets with varying properties is used to expose the strengths and weaknesses of each technique. Finally, a robust clustering technique is discussed based on reaching a consensus among the multiple approaches, overcoming the weaknesses found individually.

physics.data-an↗
arXiv2017

Dynamics on the Double Morse Potential: A Paradigm for Roaming Reactions with no Saddle Points

In this paper we analyze a two degree of freedom Hamiltonian system constructed from two planar Morse potentials. The resulting potential energy surface has two potential wells surrounded by an unbounded flat region containing no critical points. In addition, the model has an index one saddle between the potential wells. We study the dynamical mechanisms underlying transport between the two potential wells, with emphasis on the role of the flat region surrounding the wells. The model allows us to probe many of the features of the roaming mechanism whose reaction dynamics are of current interest in the chemistry community.

physics.chem-ph↗
arXiv2017

Lagrangian Descriptors for Two Dimensional, Area Preserving, Autonomous and Nonautonomous Maps

In this paper we generalize the method of Lagrangian descriptors to two dimensional, area preserving, autonomous and nonautonomous discrete time dynamical systems. We consider four generic model problems--a hyperbolic saddle point for a linear, area-preserving autonomous map, a hyperbolic saddle point for a nonlinear, area-preserving autonomous map, a hyperbolic saddle point for linear, area-preserving nonautonomous map, and a hyperbolic saddle point for nonlinear, area-preserving nonautonomous map. The discrete time setting allows us to evaluate the expression for the Lagrangian descriptors explicitly for a certain class of norms. This enables us to provide a rigorous setting for the notion that the "singular sets'' of the Lagrangian descriptors correspond to the stable and unstable manifolds of hyperbolic invariant sets, as well as to understand how this depends upon the particular norms that are used. Finally we analyze, from the computational point of view, the performance of this tool for general nonlinear maps, by computing the "chaotic saddle'' for autonomous and nonautonomous versions of the Hénon map.

math.DS↗
arXiv2017

The Chaotic Saddle in the Lozi map, autonomous and non-autonomous versions

In this paper we prove the existence of a chaotic saddle for a piecewise linear map of the plane, referred to as the Lozi map. We study the Lozi map in its orientation and area preserving version. First, we consider the autonomous version of the Lozi map to which we apply the Conley-Moser conditions to obtain the proof of a chaotic saddle. Then we generalize the Lozi map on a non-autonomous version and we prove that the first and the third Conley-Moser conditions are satisfied, which imply the existence of a chaotic saddle. Finally, we numerically demonstrate how the structure of this nonautonomous chaotic saddle varies as parameters are varied.

math.DS↗
arXiv2017

Lagrangian Descriptors for Stochastic Differential Equations: A Tool for Revealing the Phase Portrait of Stochastic Dynamical Systems

In this paper we introduce a new technique for depicting the phase portrait of stochastic differential equations. Following previous work for deterministic systems, we represent the phase space by means of a generalization of the method of Lagrangian descriptors to stochastic differential equations. Analogously to the deterministic differential equations setting, the Lagrangian descriptors graphically provide the distinguished trajectories and hyperbolic structures arising within the stochastic dynamics, such as random fixed points and their stable and unstable manifolds. We analyze the sense in which structures form barriers to transport in stochastic systems. We apply the method to several benchmark examples where the deterministic phase space structures are well-understood. In particular, we apply our method to the noisy saddle, the stochastically forced Duffing equation, and the stochastic double gyre model that is a benchmark for analyzing fluid transport.

math.DS↗
arXiv2017

Chaotic Dynamics in Nonautonomous Maps: Application to the Nonautomous Henon Map

In this paper we analyze chaotic dynamics for two dimensional nonautonomous maps through the use of a nonautonomous version of the Conley-Moser conditions given previously. With this approach we are able to give a precise definition of what is meant by a chaotic invariant set for nonautonomous maps. We extend the nonautonomous Conley-Moser conditions by deriving a new sufficient condition for the nonautonomous chaotic invariant set to be hyperbolic. We consider the specific example of a nonautonomous Hénon map and give sufficient conditions, in terms of the parameters defining the map, for the nonautonomous Hénon map to have a hyperbolic chaotic invariant set.

math.DS↗
arXiv2017

A Theoretical Framework for Lagrangian Descriptors

This paper provides a theoretical background for Lagrangian Descriptors (LDs). The goal of achieving rigourous proofs that justify the ability of LDs to detect invariant manifolds is simplified by introducing an alternative definition for LDs. The definition is stated for $n$-dimensional systems with general time dependence, however we rigorously prove that this method reveals the stable and unstable manifolds of hyperbolic points in four particular 2D cases: a hyperbolic saddle point for linear autonomous systems, a hyperbolic saddle point for nonlinear autonomous systems, a hyperbolic saddle point for linear nonautonomous systems and a hyperbolic saddle point for nonlinear nonautonomous systems. We also discuss further rigorous results which show the ability of LDs to highlight additional invariants sets, such as $n$-tori. These results are just a simple extension of the ergodic partition theory which we illustrate by applying this methodology to well-known examples, such as the planar field of the harmonic oscillator and the 3D ABC flow. Finally, we provide a thorough discussion on the requirement of the objectivity (frame-invariance) property for tools designed to reveal phase space structures and their implications for Lagrangian descriptors.

math.DS↗
arXiv2016

Integrability and strong normal forms for non-autonomous systems in a neighbourhood of an equilibrium

The paper deals with the problem of existence of a convergent "strong" normal form in the neighbourhood of an equilibrium, for a finite dimensional system of differential equations with analytic and time-dependent non-linear term. The problem can be solved either under some non-resonance hypotheses on the spectrum of the linear part or if the non-linear term is assumed to be (slowly) decaying in time. This paper "completes" a pioneering work of Pustil'nikov in which, despite under weaker non-resonance hypotheses, the nonlinearity is required to be asymptotically autonomous. The result is obtained as a consequence of the existence of a strong normal form for a suitable class of real-analytic Hamiltonians with non-autonomous perturbations.

math.DS↗
arXiv2015

Phase space barriers and dividing surfaces in the absence of critical points of the potential energy: Application to roaming in ozone

We examine the phase space structures that govern reaction dynamics in the absence of critical points on the potential energy surface. We show that in the vicinity of hyperbolic invariant tori it is possible to define phase space dividing surfaces that are analogous to the dividing surfaces governing transition from reactants to products near a critical point of the potential energy surface. We investigate the problem of capture of an atom by a diatomic molecule and show that a normally hyperbolic invariant manifold exists at large atom-diatom distances, away from any critical points on the potential. This normally hyperbolic invariant manifold is the anchor for the construction of a dividing surface in phase space, which defines the outer or loose transition state governing capture dynamics. We present an algorithm for sampling an approximate capture dividing surface, and apply our methods to the recombination of the ozone molecule. We treat both 2 and 3 degree of freedom models with zero total angular momentum. We have located the normally hyperbolic invariant manifold from which the orbiting (outer) transition state is constructed. This forms the basis for our analysis of trajectories for ozone in general, but with particular emphasis on the roaming trajectories.

physics.chem-ph↗
arXiv2015

Negligibility of small divisor effects in the normal form theory for nearly-integrable Hamiltonians with decaying non-autonomous perturbations

The paper deals with the problem of the existence of a normal form for a nearly-integrable real-analytic Hamiltonian with aperiodically time-dependent perturbation decaying (slowly) in time. In particular, in the case of an isochronous integrable part, the system can be cast in an exact normal form, regardless of the properties of the frequency vector. The general case is treated by a suitable adaptation of the finite order normalization techniques usually used for Nekhoroshev arguments. The key point is that the so called "geometric part" is not necessary in this case. As a consequence, no hypotheses on the integrable part are required, apart from analyticity. The work, based on two different perturbative approaches developed by A.Giorgilli et al., is a generalisation of the techniques used by the same authors to treat more specific aperiodically time-dependent problems.

math.DS↗
arXiv2014

A Kolmogorov theorem for nearly-integrable Poisson systems with asymptotically decaying time-dependent perturbation

The aim of this paper is to prove the Kolmogorov theorem of persistence of Diophantine flows for nearly-integrable Poisson systems associated to a real analytic Hamiltonian with aperiodic time dependence, provided that the perturbation is asymptotically vanishing. The paper is an extension of an analogous result by the same authors for canonical Hamiltonian systems; the flexibility of the Lie series method developed by A. Giorgilli et al., is profitably used in the present generalisation.

math.DS↗
arXiv2014

The Role of Variability in Transport for Large-Scale Flow Dynamics

We develop a framework to study the role of variability in transport across a streamline of a reference flow. Two complementary schemes are presented: a graphical approach for individual cases, and an analytical approach for general properties. The spatially nonlinear interaction of dynamic variability and the reference flow results in flux variability. The characteristic time-scale of the dynamic variability and the length-scale of the flux variability in a unit of flight-time govern the spatio-temporal interaction that leads to transport. The non-dimensional ratio of the two characteristic scales is shown to be a a critical parameter. The pseudo-lobe sequence along the reference streamline describes spatial coherency and temporal evolution of transport. For finite-time transport from an initial time up to the present, the characteristic length-scale of the flux variability regulates the width of the pseudo-lobes. The phase speed of pseudo-lobe propagation averages the reference flow and the flux variability. In contrast, for definite transport over a fixed time interval and spatial segment, the characteristic time-scale of the dynamic variability regulates the width of the pseudo-lobes. Generation of the pseudo-lobe sequence appears to be synchronous with the dynamic variability, although it propagates with the reference flow. In either case, the critical characteristic ratio is found to be one, corresponding to a resonance of the flux variability with the reference flow. Using a kinematic model, we demonstrate the framework for two types of transport in a blocked flow of the mid-latitude atmosphere: across the meandering jet axis and between the jet and recirculating cell.

physics.flu-dyn↗
arXiv2014

Persistence of Diophantine flows for quadratic nearly-integrable Hamiltonians under slowly decaying aperiodic time dependence

The aim of this paper is to prove a Kolmogorov-type result for a nearly-integrable Hamiltonian, quadratic in the actions, with an aperiodic time dependence. The existence of a torus with a prefixed Diophantine frequency is shown in the forced system, provided that the perturbation is real-analytic and (exponentially) decaying with time. The advantage consists of the possibility to choose an arbitrarily small decaying coefficient, consistently with the perturbation size.

math.DS↗
arXiv2014

Nonstatistical dynamics on the caldera

We explore both classical and quantum dynamics of a model potential exhibiting a caldera: that is, a shallow potential well with two pairs of symmetry related index one saddles associated with entrance/exit channels. Classical trajectory simulations at several different energies confirm the existence of the `dynamical matching' phenomenon originally proposed by Carpenter, where the momentum direction associated with an incoming trajectory initiated at a high energy saddle point determines to a considerable extent the outcome of the reaction (passage through the diametrically opposing exit channel). By studying a `stretched' version of the caldera model, we have uncovered a generalized dynamical matching: bundles of trajectories can reflect off a hard potential wall so as to end up exiting predominantly through the transition state opposite the reflection point. We also investigate the effects of dissipation on the classical dynamics. In addition to classical trajectory studies, we examine the dynamics of quantum wave packets on the caldera potential (stretched and unstretched). These computations reveal a quantum mechanical analogue of the `dynamical matching' phenomenon, where the initial expectation value of the momentum direction for the wave packet determines the exit channel through which most of the probability density passes to product.

physics.chem-ph↗
arXiv2014

Roaming dynamics in Ketene isomerization

A reduced two dimensional model is used to study Ketene isomerization reaction. In light of recent results by Ulusoy \textit{et al.} [J.\ Phys.\ Chem.\ A {\bf 117}, 7553 (2013)], the present work focuses on the generalization of the roaming mechanism to the Ketene isomerization reaction by applying our phase space approach previously used to elucidate the roaming phenomenon in ion-molecule reactions. Roaming is again found be associated with the trapping of trajectories in a phase space region between two dividing surfaces; trajectories are classified as reactive or nonreactive, and are further naturally classified as direct or non-direct (roaming). The latter long-lived trajectories are trapped in the region of non-linear mechanical resonances, which in turn define alternative reaction pathways in phase space. It is demonstrated that resonances associated with periodic orbits provide a dynamical explanation of the quantum mechanical resonances found in the isomerization rate constant calculations by Gezelter and Miller [J.\ Chem.\ Phys.\ {\bf 103}, 7868-7876 (1995)]. Evidence of the trapping of trajectories by `sticky' resonant periodic orbits is provided by plotting Poincaré surfaces of section, and a gap time analysis is carried out in order to investigate the statistical assumption inherent in transition state theory for Ketene isomerization.

physics.chem-ph↗