N. De Leon

Semiclassical quantization and extraction of eigenfunctions using arbitrary trajectories

We present in this paper a coordinate independent semiclassical quantization method. We demonstrate that in order to extract accurate eigenvalues and eigenfunctions the trajectory does not necessarily have to reside on the quantizing torus, rather, one can use information obtained on arbitrary tori. Because the method is coordinate independent, no difficulty is encountered in quantizing within classical resonance zones. Furthermore, nearby eigenstates and eigenvalues (nearby in action space) may be extracted from the same trajectory—this is especially convenient when the density of states becomes large.

Semiclassical spectral quantization: Application to two and four coupled molecular degrees of freedom

Semiclassical quantization of the quasiperiodic vibrational motion of molecules is usually based on Einstein–Brillouin–Keller (EBK) conditions for the quantization of the classical actions. Explicit use of the EBK conditions for molecular systems of K degrees of freedom requires K quantization conditions. Therefore, explicit use of the EBK conditions becomes increasingly difficult if not impossible for polyatomic systems of three or more degrees of freedom. In this paper we propose a semiclassical quantization method which makes explicit use of phase coherence of the de Broglie wave associated with the trajectory rather than the EBK conditions. We show that taking advantage of phase coherence reduces the K quantization conditions to a single quantum condition—regardless of the number of degrees of freedom. For reasons that will become obvious we call this method ‘‘spectral quantization.’’ Polyatomic vibrational wave functions and energy eigenvalues are generated from quasiperiodic classical trajectories. ...

Cylindrical manifolds in phase space as mediators of chemical reaction dynamics and kinetics. I. Theory

A microcanonical kinetic theory of reactions based upon the structure within phase space is developed. It is shown that the dynamics of reaction across an energetic barrier is mediated by invariant manifolds embedded in phase space that have the geometry of simple cylinders. The ideas are developed by considering molecular systems modeled by two vibrational degrees of freedom, a reaction coordinate and a ‘‘bath’’ coordinate. The kinetic theory is constructed by focusing on the dynamics between n mapping planes (‘‘n‐map’’) and the ‘‘reactive island’’ (RI) structure within them. We discuss how the structure of the conformer population decay in isomerization reactions can be obtained from the RI kinetic model. Formal solutions of the kinetic equations are discussed with specific attention given towards the calculation of the isomerization reaction rate. The formal theory is developed in Paper I of this series. Numerical considerations and applications to the reaction dynamics of model molecular systems with ...

Fourier transform methods for calculating action variables and semiclassical eigenvalues for coupled oscillator systems

Two methods for calculating the good action variables and semiclassical eigenvalues for coupled oscillator systems are presented, both of which relate the actions to the coefficients appearing in the Fourier representation of the normal coordinates and momenta. The two methods differ in that one is based on the exact expression for the actions together with the EBK semiclassical quantization condition while the other is derived from the Sorbie–Handy (SH) approximation to the actions. However, they are also very similar in that the actions in both methods are related to the same set of Fourier coefficients and both require determining the perturbed frequencies in calculating actions. These frequencies are also determined from the Fourier representations, which means that the actions in both methods are determined from information entirely contained in the Fourier expansion of the coordinates and momenta. We show how these expansions can very conveniently be obtained from fast Fourier transform (FFT) method...

Quantum manifestations of classical resonance zones

We examine the concept of nodal breakup of wave functions as a criterion for quantum mechanical ergodicity. We find that complex nodal structure of wave functions is not sufficient to determine quantum mechanical ergodicity. The influence of classical resonances [which manifest themselves as classical resonance zones (CRZ)] may also be responsible for the seeming complexity of nodal structure. We quantify this by reexamining one of the two systems studied by Stratt, Handy, and Miller [J. Chem. Phys. 71, 3311 (1974)] from both a quantum mechanical and classical point of view. We conclude that quasiperiodic classical motion can account for highly distorted quantum eigenstates. One should always keep this in mind when addressing questions regarding quantum mechanical ergodicity.

Cylindrical manifolds and reactive island kinetic theory in the time domain

In a series of recent publications we discussed the concept of cylindrical manifolds and their role in mediating the reaction dynamics of chemical reactions. The cylindrical manifolds were used to develop a chemical reaction rate theory we called reactive island (RI) theory. RI theory was cast in terms of the map dynamics between n Poincare mapping planes—which were referred to as the ‘‘n‐map.’’ Therefore ‘‘time’’ did not explicitly appear within n‐map RI theory. In this paper we extend n‐map RI theory to the time domain. The formal theory, cast as a master equation, is used to obtain the temporal RI model. Temporal RI theory is applied to a two degree‐of‐freedom system exhibiting dynamical chaos. The results of temporal RI theory are compared with classical Rice–Ramsberger–Kassel–Marcus (RRKM) theory and it is found that even under, presumably, ‘‘ideal’’ dynamical conditions, RRKM theory can be in serious error with numerical simulation. It is also seen that temporal RI theory accurately accounts for the...

Geometry and dynamics of stable and unstable cylinders in Hamiltonian systems

Abstract Stable and unstable manifolds in phase space with an S 1 × R 1 (cylindrical) geometry are shown to exist for certain two degree of freedom Hamiltonian systems. Specific attention is given to Hamiltonian systems with potential barriers, although the concepts developed are more general. The existence of these cylinders is independent of the nature of the Hamiltonian dynamics (i.e. regular or chaotic). A detailed discussion is given where we show that appropriate Poincare sections of the cylinders yield a map structure (which we denote as “reactive islands”) that is distinct from the usual homoclinic tangle. The cylinders have the physical property that all motion across a barrier must occur through the interior of these surfaces. The cylinders thus mediate the reaction dynamics. A kinetic mechanism based upon the properties of the cylinders is developed and tested against several numerical simulations of the reaction dynamics of a model Hamiltonian system. The threshold limiting form of the standard theory of microcanonical reaction rates is derived.

Reactive islands as essential mediators of unimolecular conformational isomerization: A dynamical study of 3‐phospholene

In this paper we focus on the detailed nonlinear classical dynamics of conformational isomerization. In particular we concentrate on systems which admit phase space structures we call ‘‘reactive islands.’’ Our calculations are on a two degree of freedom model of the molecule 3‐phospholene with an experimentally fit potential energy surface by Harthcock and Laane. The reactive islands (RIS) are embedded within and are part of chaotic regions of phase space. We find that the RIS are constructed from a linear stability analysis of the period 1 orbit at the transition state or approximated by a similar analysis on reactive periodic orbits. The two approaches converge as the order of the reactive periodic orbit increases. It is found that the fully constructed RIS have well defined regions of reactivity and thus mediate the process of conformational isomerization.The overlap areas of the RIS give important kinetic information such as probabilities for trapped to reactive motion, reactive to trapped motion, and...

Cylindrical manifolds in phase space as mediators of chemical reaction dynamics and kinetics. II. Numerical considerations and applications to models with two degrees of freedom

In Paper I we discussed the existence of cylindrical manifolds embedded in phase space which mediate the dynamics of chemical reactions. A kinetic theory of population decays and decay rate constants was developed which we called ‘‘reactive island’’ (RI) theory. In this paper we discuss the details of the numerical implementation of the theory and then apply it to several molecular models (with two coupled degrees of freedom) representing isomerization between two and three states. Numerical simulations of population decays and asymptotic decay rate constants are compared to the RI theoretical predictions as well as the predictions from the Purely Random Theory (PRT) and Transition State Theory (TST) of reactions. Of the ten systems studied we find that RI theory is generally in good to excellent agreement with the numerical simulations. Only one system exhibits significant deviation between the RI and numerical results. This deviation is seen to be a result of a strong intraconformer dynamical bottleneck...

Order in chaos and the dynamics and kinetics of unimolecular conformational isomerization

A high degree of structure and therefore order in chaos is found to exist in the detailed dynamical pathways to conformational isomerization. It is shown that this structure can be used to determine the probabilities associated with the dynamical pathways to reaction, trapping, and back reaction. An earlier publication described the mediation of the dynamics of 3‐phospholene by phase space structures we called ‘‘reactive islands’’ (RIS)21. In this paper we extend the physical and mathematical properties of RIS and develop the corresponding kinetic theory. RIS theory is applied to a model of a hindered rotor and 3‐phospholene. It is shown that the RIS kinetic model accurately predicts trajectory simulations of conformer population decay. Comparisons with standard RRKM theory are included. A discussion on the extension of RIS theory to quantum reactive dynamics and its relevance to laboratory experiments is also included.A high degree of structure and therefore order in chaos is found to exist in the detailed dynamical pathways to conformational isomerization. It is shown that this structure can be used to determine the probabilities associated with the dynamical pathways to reaction, trapping, and back reaction. An earlier publication described the mediation of the dynamics of 3‐phospholene by phase space structures we called ‘‘reactive islands’’ (RIS)21. In this paper we extend the physical and mathematical properties of RIS and develop the corresponding kinetic theory. RIS theory is applied to a model of a hindered rotor and 3‐phospholene. It is shown that the RIS kinetic model accurately predicts trajectory simulations of conformer population decay. Comparisons with standard RRKM theory are included. A discussion on the extension of RIS theory to quantum reactive dynamics and its relevance to laboratory experiments is also included.