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Physical Review A

Towards many-dimensional real-time quantum theory for heavy-particle dynamics. I. Semiclassics in the Lagrange picture of classical phase flow

Satoshi Takahashi, Kazuo Takatsuka

Published Jan 14, 2014• 14 citations
Publisher

Abstract

We study a quantum theory in terms of action decomposed function (ADF), a class of quantum wave function, towards many-dimensional applications to quantum dynamics of heavy particles as in chemical reactions. The equation of motion for the complex-valued amplitude of ADF represents a coupling between the internal diffusive motion of a wave packet and dynamics of its group velocity in a hierarchical manner ascending from classical to purely quantum mechanics via semiclassical dynamics. We attempt to solve this equation of motion dividing it into two stages: a semiclassical level and beyond. In this paper, as the first stage, we develop a semiclassical approximation in the Lagrange picture of classical phase flow. In the Euler picture (as in the standard WKB picture), continuous integration of the stability matrix along the paths is required. By adopting the Lagrange picture, on the other hand, we represent the semiclassical amplitude in terms of what we call deviation determinant, which can be evaluated readily in many-dimensional systems. Numerical tests show that ADF reproduces quantum wave packets at each space-time point along classical paths very well. However, the ADF in this stage is not free of the semiclassical singularity. In other words, the wave functions diverge at turning points or caustics, depending on the initial conditions chosen. This divergence is known to take place at points where classical paths smoothly distributed in phase space have ``focuses'' in configuration space (or momentum space) and reflects an intrinsic relationship between quantum and classical mechanics. Therefore, it is by studying the mechanism of removing the singularity that the essential feature of quantum mechanics will be clarified. This aspect will be discussed in a companion paper [K. Takatsuka and S. Takahashi, Phys. Rev. A 89, 012109 (2014)] as the second stage of many-body quantum theory.

DOI
10.1103/physreva.89.012108

Related papers

Towards many-dimensional real-time quantum theory for heavy-particle dynamics. II. Beyond semiclassics by quantum smoothing of the singularity in quantum-classical correspondence

Kazuo Takatsuka, Satoshi Takahashi

A theory of many-dimensional real-time quantum dynamics is studied in terms of action decomposed function (ADF), a class of quantum wave function. In the preceding companion paper [S. Takahashi and K. Takatsuka, Phys. Rev. A 89, 012108 (2014)], we showed that semiclassical dynamics for ADF in the Lagrange picture of phase flow can be described in terms of what we call deviation determinant and associated quantum phases without use of the stability matrix. Consequently, the Hessian of the involved potential functions is not required in this formalism. This paper is devoted to an analysis of the mechanism of quantum diffusion (quantum smoothing) that removes the singularity inherent in the semiclassical ADF: We derive a Lorentzian form for the amplitude factor of ADF. The real part of its denominator comes from the deviation determinant, while the imaginary part reflects quantum diffusion and is proportional to the Planck constant. The presence of the nonzero imaginary part smooths out the singularity and removes the divergence. Besides, this imaginary part can be obtained through a Wronskian relation with the deviation vectors, which can be solved rather easily at each space-time point on a classical trajectory. A number of theoretical advantages of the Lorentzian form and the Wronskian relation are illustrated theoretically and numerically. It turns out that there is no essential difficulty in applications to many-dimensional heavy-particle systems such as molecules. The theory is examined with stringent numerical tests.

Physical Review A•Jan 14, 2014•15 citations

Semiclassical theory for the Maslov-type wave packet: Hierarchy below the semiclassical Feynman kernel

Atsuko Inoue-Ushiyama, Kazuo Takatsuka

A semiclassical theory based on the Maslov-type wave packet is reported. The present approximation constitutes a class of semiclassical theory that brings about a hierarchy of theoretical structures below or equivalent to the standard semiclassical approximation to the Feynman kernel. We first propose a semiclassical wave function; that is, what we call the action-decomposed function (ADF). An ADF is propagated in time semiclassically along a ``single action surface,'' which is characterized in terms of a given initial momentum, with the phase being proportional to the ${F}_{2}(q,p)$-type generating function. An arbitrary wave function can be expanded continuously in the ADF's of different initial momenta, each of which is associated with weighting factors both in configuration and momentum spaces. Depending on the form of the weighting function, the present scheme covers a number of different levels of approximation, ranging from a ``single'' ADF to a semiclassical kernel. Thus our theory provides a way of connecting the Maslov-type semiclassical wave packet to the WKB theory based on the Feynman kernel. It is generally concluded that the above kernel limit attains the highest accuracy possible within the present scheme, but it requires a large number of classical trajectories to represent it. On the other hand, a single ADF yields a little less accurate results but demands the fewest representing classical trajectories due to the narrowest momentum distribution. In fact, we show numerically that the autocorrelation function represented in terms of a single ADF, from which the energy spectrum is extracted with a Fourier transformation, can be calculated with drastically fewer classical trajectories without losing much accuracy. We also present a limitation in applying the ADF, and show an interesting symptom arising from a pathological use of the approximation. The present theory is quite promising for a spectral analysis of the vibrational states of relatively large molecules, if applied appropriately.

Physical Review A•May 1, 1999•27 citations

Phase-space representation of quantum mechanics and its relation to phase-space path integrals

Kazuo Takatsuka

A detailed framework for a new formalism of phase-space path integral is presented, the outline of the theory of which has been reported elsewhere [K. Takatsuka, Phys. Rev. Lett. 61, 503 (1988)]. This path integral is described in terms of a phase-space distribution function, which was proposed earlier by the present author under the name of the dynamical characteristic function (DCF). The DCF is characterized by two independent wave functions and with two phase spaces. In the present paper, we extend the DCF by utilizing the Feynman kernel in place of the two independent wave functions. This is called the identity DCF. The dynamics of the DCF for general wave packets is reduced to that of the identity DCF. Some characteristics of the identity DCF are presented. For example, the quantum-mechanical time-evolution operator is represented in terms of the identity DCF and of a complete set of quantum q (coordinate) and p (momentum) operators. A semiclassical theory for the identity DCF is also developed, its primary aim being the study of heavy-particle dynamics such as molecular collisions.It is shown that the propagation of the identity DCF is represented by classical trajectories, each of which is associated with an amplitude factor and with the action integral as the quantum phase factor. This amplitude factor is free from singularity, unlike the primitive semiclassical expression of the Feynman kernel, which is well known to diverge at caustics. The physical significance of the identity DCF is analyzed in the context of chaotic dynamics. In particular, it is shown that its amplitude factor is an explicit function of the eigenvalues of a Jacobian matrix [\ensuremath{\partial}(${\mathit{q}}_{\mathit{f}}$,${\mathit{p}}_{\mathit{f}}$)/\ensuremath{\partial}(${\mathit{q}}_{\mathit{i}}$,${\mathit{p}}_{\mathit{i}}$)], where (${\mathit{q}}_{\mathit{i}}$,${\mathit{p}}_{)}$ and (${q}_{f}$,${p}_{f}$) are the initial and final points, respectively, of a classical trajectory. These eigenvalues are well known in the study of the classical chaos of Hamilton systems and have been used to construct a measure of the linear (and local) stability of an orbit, the Liapounov characteristic exponents, and so on. Further, if the identity DCF is applied to a periodic orbit, the amplitude factor becomes equivalent to the square root of the determinant of a matrix, which is the so-called monodromy matrix minus the unit matrix. This matrix is one of the standard quantities used in bifurcation theory to investigate the stability of fixed points. In fact, the amplitude factor is closely related to the so-called residue, which was proposed by Greene [J. Math. Phys. 20, 1183 (1979)] in order to predict the occurrence of global chaos in classical systems. It is emphasized that all these classical quantities arise naturally in our representation of quantum mechanics.

Physical Review A•Jun 1, 1989•15 citations

Time-dependent approach to semiclassical dynamics

Eric J. Heller

In this paper we develop a new approach to semiclassical dynamics which exploits the fact that extended wavefunctions for heavy particles (or particles in harmonic potentials) may be decomposed into time−dependent wave packets, which spread minimally and which execute classical or nearly classical trajectories. A Gaussian form for the wave packets is assumed and equations of motion are derived for the parameters characterizing the Gaussians. If the potential (which may be nonseparable in many coordinates) is expanded in a Taylor series about the instantaneous center of the (many−particle) wave packet, and up to quadratic terms are kept, we find the classical parameters of the wave packet (positions, momenta) obey Hamilton’s equation of motion. Quantum parameters (wave packet spread, phase factor, correlation terms, etc.) obey similar first order quantum equations. The center of the wave packet is shown to acquire a phase equal to the action integral along the classical path. State−specific quantum information is obtained from the wave packet trajectories by use of the superposition principle and projection techniques. Successful numerical application is made to the collinear He + H2 system widely used as a test case. Classically forbidden transitions are accounted for and obtained in the same manner as the classically allowed transitions; turning points present no difficulties and flux is very nearly conserved.

The Journal of Chemical Physics•Feb 15, 1975•1,619 citations

Generalized Gaussian wave packet dynamics, Schrödinger equation, and stationary phase approximation

Daniel Huber, Eric J. Heller, Robert G. Littlejohn

We have recently published a new semiclassical method, generalized Gaussian wave packet dynamics, which extends Gaussian wave packet dynamics into complex phase space. Although we were able to give an accurate formulation of the method, we had at the time of writing that paper only an intuitive, heuristic understanding of the deeper causes which make the method work. A more mathematical understanding was needed. To close this gap we show in this paper the equivalence of the new method with a first order expansion of ℏ of the Schrödinger equation. We further prove that the new method is equivalent to the stationary phase approximation, using the usual WKB formula for the propagator. The latter equivalence enables us to show that all the symmetry properties of time-dependent quantum mechanics also hold in the new semiclassical theory. Finally, we provide some elaboration of the method, and clarify several issues that were not discussed before. With this new insight we are able to formulate a simple rule for the calculation of semiclassical wave functions that contain contributions from more than one branch. This corrects for the divergence of semiclassical wave functions near caustics, a problem that we encountered in the preceding paper.

The Journal of Chemical Physics•Aug 15, 1988•118 citations

Classical mechanics and the spreading of localized wave packets in condensed phase molecular systems

Michael F. Herman, D. F. Coker

The relationship between the diverging of classical trajectories in chaotic many-body systems, the spreading of quantum wave packets, and the validity and use of classical molecular dynamics is explored. This analysis, which is based on the semiclassical description of wave function propagation in terms of a weighted integration over a traveling fixed width coherent state basis, suggests that the exponential divergence of nearby classical trajectories in chaotic many-body systems should result in the rapid delocalization of an initially localized quantum wave packet describing the state of the system. Thus the justification for the use of classical molecular dynamics procedures for these supposedly classical systems cannot be based on the picture of the system wave function remaining localized as its center follows a nearly classical trajectory. The quantum evolution of the system density, on the other hand, requires two propagators, and each of these propagators is represented as an integration over trajectories in the semiclassical picture. The interference between the contributions from these two integrations over classical trajectories focuses the analysis on the most important points in this trajectory pair space, which are shown to occur when both trajectories in the pair are the same. Given reasonable assumptions for the initial density for a system that is expected to be well described by classical molecular dynamics, and given an appropriate choice for the width of the coherent state basis which is employed in the semiclassical description, it is shown that the semiclassical expressions for time dependent observables and correlation functions reduce the purely classical expressions, despite the fact that an initially localized wave packet would rapidly delocalize for the same system.

The Journal of Chemical Physics•Aug 1, 1999•43 citations
We study a quantum theory in terms of action decomposed function (ADF), a class of quantum wave function, towards many-dimensional applications to quantum dynamics of heavy particles as in chemical reactions. The equation of motion for the complex-valued amplitude of ADF represents a coupling between the internal diffusive motion of a wave packet and dynamics of its group velocity in a hierarchical manner ascending from classical to purely quantum mechanics via semiclassical dynamics. We attempt to solve this equation of motion dividing it into two stages: a semiclassical level and beyond. In this paper, as the first stage, we develop a semiclassical approximation in the Lagrange picture of classical phase flow. In the Euler picture (as in the standard WKB picture), continuous integration of the stability matrix along the paths is required. By adopting the Lagrange picture, on the other hand, we represent the semiclassical amplitude in terms of what we call deviation determinant, which can be evaluated readily in many-dimensional systems. Numerical tests show that ADF reproduces quantum wave packets at each space-time point along classical paths very well. However, the ADF in this stage is not free of the semiclassical singularity. In other words, the wave functions diverge at turning points or caustics, depending on the initial conditions chosen. This divergence is known to take place at points where classical paths smoothly distributed in phase space have ``focuses'' in configuration space (or momentum space) and reflects an intrinsic relationship between quantum and classical mechanics. Therefore, it is by studying the mechanism of removing the singularity that the essential feature of quantum mechanics will be clarified. This aspect will be discussed in a companion paper [K. Takatsuka and S. Takahashi, Phys. Rev. A 89, 012109 (2014)] as the second stage of many-body quantum theory.
A theory of many-dimensional real-time quantum dynamics is studied in terms of action decomposed function (ADF), a class of quantum wave function. In the preceding companion paper [S. Takahashi and K. Takatsuka, Phys. Rev. A 89, 012108 (2014)], we showed that semiclassical dynamics for ADF in the Lagrange picture of phase flow can be described in terms of what we call deviation determinant and associated quantum phases without use of the stability matrix. Consequently, the Hessian of the involved potential functions is not required in this formalism. This paper is devoted to an analysis of the mechanism of quantum diffusion (quantum smoothing) that removes the singularity inherent in the semiclassical ADF: We derive a Lorentzian form for the amplitude factor of ADF. The real part of its denominator comes from the deviation determinant, while the imaginary part reflects quantum diffusion and is proportional to the Planck constant. The presence of the nonzero imaginary part smooths out the singularity and removes the divergence. Besides, this imaginary part can be obtained through a Wronskian relation with the deviation vectors, which can be solved rather easily at each space-time point on a classical trajectory. A number of theoretical advantages of the Lorentzian form and the Wronskian relation are illustrated theoretically and numerically. It turns out that there is no essential difficulty in applications to many-dimensional heavy-particle systems such as molecules. The theory is examined with stringent numerical tests.
A semiclassical theory based on the Maslov-type wave packet is reported. The present approximation constitutes a class of semiclassical theory that brings about a hierarchy of theoretical structures below or equivalent to the standard semiclassical approximation to the Feynman kernel. We first propose a semiclassical wave function; that is, what we call the action-decomposed function (ADF). An ADF is propagated in time semiclassically along a ``single action surface,'' which is characterized in terms of a given initial momentum, with the phase being proportional to the F2(q,p){F}_{2}(q,p)F2​(q,p)-type generating function. An arbitrary wave function can be expanded continuously in the ADF's of different initial momenta, each of which is associated with weighting factors both in configuration and momentum spaces. Depending on the form of the weighting function, the present scheme covers a number of different levels of approximation, ranging from a ``single'' ADF to a semiclassical kernel. Thus our theory provides a way of connecting the Maslov-type semiclassical wave packet to the WKB theory based on the Feynman kernel. It is generally concluded that the above kernel limit attains the highest accuracy possible within the present scheme, but it requires a large number of classical trajectories to represent it. On the other hand, a single ADF yields a little less accurate results but demands the fewest representing classical trajectories due to the narrowest momentum distribution. In fact, we show numerically that the autocorrelation function represented in terms of a single ADF, from which the energy spectrum is extracted with a Fourier transformation, can be calculated with drastically fewer classical trajectories without losing much accuracy. We also present a limitation in applying the ADF, and show an interesting symptom arising from a pathological use of the approximation. The present theory is quite promising for a spectral analysis of the vibrational states of relatively large molecules, if applied appropriately.
A detailed framework for a new formalism of phase-space path integral is presented, the outline of the theory of which has been reported elsewhere [K. Takatsuka, Phys. Rev. Lett. 61, 503 (1988)]. This path integral is described in terms of a phase-space distribution function, which was proposed earlier by the present author under the name of the dynamical characteristic function (DCF). The DCF is characterized by two independent wave functions and with two phase spaces. In the present paper, we extend the DCF by utilizing the Feynman kernel in place of the two independent wave functions. This is called the identity DCF. The dynamics of the DCF for general wave packets is reduced to that of the identity DCF. Some characteristics of the identity DCF are presented. For example, the quantum-mechanical time-evolution operator is represented in terms of the identity DCF and of a complete set of quantum q (coordinate) and p (momentum) operators. A semiclassical theory for the identity DCF is also developed, its primary aim being the study of heavy-particle dynamics such as molecular collisions.It is shown that the propagation of the identity DCF is represented by classical trajectories, each of which is associated with an amplitude factor and with the action integral as the quantum phase factor. This amplitude factor is free from singularity, unlike the primitive semiclassical expression of the Feynman kernel, which is well known to diverge at caustics. The physical significance of the identity DCF is analyzed in the context of chaotic dynamics. In particular, it is shown that its amplitude factor is an explicit function of the eigenvalues of a Jacobian matrix [\ensuremath{\partial}(qf{\mathit{q}}_{\mathit{f}}qf​,pf{\mathit{p}}_{\mathit{f}}pf​)/\ensuremath{\partial}(qi{\mathit{q}}_{\mathit{i}}qi​,pi{\mathit{p}}_{\mathit{i}}pi​)], where (qi{\mathit{q}}_{\mathit{i}}qi​,p){\mathit{p}}_{)}p)​ and (qf{q}_{f}qf​,pf{p}_{f}pf​) are the initial and final points, respectively, of a classical trajectory. These eigenvalues are well known in the study of the classical chaos of Hamilton systems and have been used to construct a measure of the linear (and local) stability of an orbit, the Liapounov characteristic exponents, and so on. Further, if the identity DCF is applied to a periodic orbit, the amplitude factor becomes equivalent to the square root of the determinant of a matrix, which is the so-called monodromy matrix minus the unit matrix. This matrix is one of the standard quantities used in bifurcation theory to investigate the stability of fixed points. In fact, the amplitude factor is closely related to the so-called residue, which was proposed by Greene [J. Math. Phys. 20, 1183 (1979)] in order to predict the occurrence of global chaos in classical systems. It is emphasized that all these classical quantities arise naturally in our representation of quantum mechanics.
In this paper we develop a new approach to semiclassical dynamics which exploits the fact that extended wavefunctions for heavy particles (or particles in harmonic potentials) may be decomposed into time−dependent wave packets, which spread minimally and which execute classical or nearly classical trajectories. A Gaussian form for the wave packets is assumed and equations of motion are derived for the parameters characterizing the Gaussians. If the potential (which may be nonseparable in many coordinates) is expanded in a Taylor series about the instantaneous center of the (many−particle) wave packet, and up to quadratic terms are kept, we find the classical parameters of the wave packet (positions, momenta) obey Hamilton’s equation of motion. Quantum parameters (wave packet spread, phase factor, correlation terms, etc.) obey similar first order quantum equations. The center of the wave packet is shown to acquire a phase equal to the action integral along the classical path. State−specific quantum information is obtained from the wave packet trajectories by use of the superposition principle and projection techniques. Successful numerical application is made to the collinear He + H2 system widely used as a test case. Classically forbidden transitions are accounted for and obtained in the same manner as the classically allowed transitions; turning points present no difficulties and flux is very nearly conserved.
We have recently published a new semiclassical method, generalized Gaussian wave packet dynamics, which extends Gaussian wave packet dynamics into complex phase space. Although we were able to give an accurate formulation of the method, we had at the time of writing that paper only an intuitive, heuristic understanding of the deeper causes which make the method work. A more mathematical understanding was needed. To close this gap we show in this paper the equivalence of the new method with a first order expansion of ℏ of the Schrödinger equation. We further prove that the new method is equivalent to the stationary phase approximation, using the usual WKB formula for the propagator. The latter equivalence enables us to show that all the symmetry properties of time-dependent quantum mechanics also hold in the new semiclassical theory. Finally, we provide some elaboration of the method, and clarify several issues that were not discussed before. With this new insight we are able to formulate a simple rule for the calculation of semiclassical wave functions that contain contributions from more than one branch. This corrects for the divergence of semiclassical wave functions near caustics, a problem that we encountered in the preceding paper.
The relationship between the diverging of classical trajectories in chaotic many-body systems, the spreading of quantum wave packets, and the validity and use of classical molecular dynamics is explored. This analysis, which is based on the semiclassical description of wave function propagation in terms of a weighted integration over a traveling fixed width coherent state basis, suggests that the exponential divergence of nearby classical trajectories in chaotic many-body systems should result in the rapid delocalization of an initially localized quantum wave packet describing the state of the system. Thus the justification for the use of classical molecular dynamics procedures for these supposedly classical systems cannot be based on the picture of the system wave function remaining localized as its center follows a nearly classical trajectory. The quantum evolution of the system density, on the other hand, requires two propagators, and each of these propagators is represented as an integration over trajectories in the semiclassical picture. The interference between the contributions from these two integrations over classical trajectories focuses the analysis on the most important points in this trajectory pair space, which are shown to occur when both trajectories in the pair are the same. Given reasonable assumptions for the initial density for a system that is expected to be well described by classical molecular dynamics, and given an appropriate choice for the width of the coherent state basis which is employed in the semiclassical description, it is shown that the semiclassical expressions for time dependent observables and correlation functions reduce the purely classical expressions, despite the fact that an initially localized wave packet would rapidly delocalize for the same system.