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 s
patially 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.
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.
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 t
he 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 Poincare 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.
A model Hamiltonian for the reaction CH$_4^+ rightarrow$ CH$_3^+$ + H, parametrized to exhibit either early or late inner transition states, is employed to investigate the dynamical characteristics of the roaming mechanism. Tight/loose transition sta
tes and conventional/roaming reaction pathways are identified in terms of time-invariant objects in phase space. These are dividing surfaces associated with normally hyperbolic invariant manifolds (NHIMs). For systems with two degrees of freedom NHIMS are unstable periodic orbits which, in conjunction with their stable and unstable manifolds, unambiguously define the (locally) non-recrossing dividing surfaces assumed in statistical theories of reaction rates. By constructing periodic orbit continuation/bifurcation diagrams for two values of the potential function parameter corresponding to late and early transition states, respectively, and using the total energy as another parameter, we dynamically assign different regions of phase space to reactants and products as well as to conventional and roaming reaction pathways. The classical dynamics of the system are investigated by uniformly sampling trajectory initial conditions on the dividing surfaces. Trajectories are classified into four different categories: direct reactive and non reactive trajectories,which lead to the formation of molecular and radical products respectively, and roaming reactive and non reactive orbiting trajectories, which represent alternative pathways to form molecular and radical products. By analysing gap time distributions at several energies we demonstrate that the phase space structure of the roaming region, which is strongly influenced by non-linear resonances between the two degrees of freedom, results in nonexponential (nonstatistical) decay.
We study reaction dynamics on a model potential energy surface exhibiting post-transition state bifurcation in the vicinity of a valley ridge inflection point. We compute fractional yields of products reached after the VRI region is traversed, both w
ith and without dissipation. It is found that apparently minor variations in the potential lead to significant changes in the reaction dynamics. Moreover, when dissipative effects are incorporated, the product ratio depends in a complicated and highly non-monotonic fashion on the dissipation parameter. Dynamics in the vicinity of the VRI point itself play essentially no role in determining the product ratio, except in the highly dissipative regime.
We provide a dynamical interpretation of the recently identified `roaming mechanism for molecular dissociation reactions in terms of geometrical structures in phase space. These are NHIMs (Normally Hyperbolic Invariant Manifolds) and their stable/uns
table manifolds that define transition states for ion-molecule association or dissociation reactions. The associated dividing surfaces rigorously define a roaming region of phase space, in which both reactive and nonreactive trajectories can be trapped for arbitrarily long times.
In this paper we study the breakdown of normal hyperbolicity and its consequences for reaction dynamics; in particular, the dividing surface, the flux through the dividing surface (DS), and the gap time distribution. Our approach is to study these qu
estions using simple, two degree-of-freedom Hamiltonian models where calculations for the different geometrical and dynamical quantities can be carried out exactly. For our examples, we show that resonances within the normally hyperbolic invariant manifold may, or may not, lead to a `loss of normal hyperbolicity. Moreover, we show that the onset of such resonances results in a change in topology of the dividing surface, but does not affect our ability to define a DS. The flux through the DS varies continuously with energy, even as the energy is varied in such a way that normal hyperbolicity is lost. For our examples the gap time distributions exhibit singularities at energies corresponding to the existence of homoclinic orbits in the DS, but these singularities are not associated with loss of normal hyperbolicity.
We investigate the fragmentation dynamics of an atomic chain under tensile stress. We have classified the location, stability type (indices) and energy of all equilibria for the general $n$-particle chain, and have highlighted the importance of saddl
e points with index $> 1$. We show that for an $n=2$-particle chain under tensile stress the index 2 saddle plays a central role in organizing the dynamics. We apply normal form theory to analyze phase space structure and dynamics in a neighborhood of the index 2 saddle. We define a phase dividing surface (DS) that enables us to classify trajectories passing through a neighborhood of the saddle point using the values of the integrals associated with the normal form. We also generalize our definition of the dividing surface and define an emph{extended dividing surface} (EDS), which is used to sample and classify all trajectories that pass through a phase space neighborhood of the index 2 saddle at total energies less than that of the saddle. Classical trajectory simulations are used to study single versus double bond breakage for the $n=2$ chain under tension. Initial conditions for trajectories are obtained by sampling the EDS at constant energy. We sample trajectories at fixed energies both above and below the energy of the saddle. The fate of trajectories (single versus double bond breakage) is explored as a function of the location of the initial condition on the EDS, and a connection made to the work of Chesnavich on collision-induced dissociation. A significant finding is that we can readily identify trajectories that exhibit bond emph{healing}. Such trajectories pass outside the nominal (index 1) transition state for single bond dissociation, but return to the potential well region, possibly several times, before ultimately dissociating.
