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The Journal of Chemical Physics

Integrating the quantum Hamilton–Jacobi equations by wavefront expansion and phase space analysis

Eric R. Bittner, Róbert E. Wyatt

Published Nov 22, 2000• 69 citations
Publisher

Abstract

In this paper we report upon our computational methodology for numerically integrating the quantum Hamilton–Jacobi equations using hydrodynamic trajectories. Our method builds upon the moving least squares method developed by Lopreore and Wyatt [Phys. Rev. Lett. 82, 5190 (1999)] in which Lagrangian fluid elements representing probability volume elements of the wave function evolve under Newtonian equations of motion which include a nonlocal quantum force. This quantum force, which depends upon the third derivative of the quantum density, ρ, can vary rapidly in x and become singular in the presence of nodal points. Here, we present a new approach for performing quantum trajectory calculations which does not involve calculating the quantum force directly, but uses the wavefront to calculate the velocity field using mv=∇S, where S/ℏ is the argument of the wave function ψ. Additional numerical stability is gained by performing local gauge transformations to remove oscillatory components of the wave function. Finally, we use a dynamical Rayleigh–Ritz approach to derive ancillary equations-of-motion for the spatial derivatives of ρ, S, and v. The methodologies described herein dramatically improve the long time stability and accuracy of the quantum trajectory approach even in the presence of nodes. The method is applied to both barrier crossing and tunneling systems. We also compare our results to semiclassical based descriptions of barrier tunneling.

DOI
10.1063/1.1319987

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In this paper we report upon our computational methodology for numerically integrating the quantum Hamilton–Jacobi equations using hydrodynamic trajectories. Our method builds upon the moving least squares method developed by Lopreore and Wyatt [Phys. Rev. Lett. 82, 5190 (1999)] in which Lagrangian fluid elements representing probability volume elements of the wave function evolve under Newtonian equations of motion which include a nonlocal quantum force. This quantum force, which depends upon the third derivative of the quantum density, ρ, can vary rapidly in x and become singular in the presence of nodal points. Here, we present a new approach for performing quantum trajectory calculations which does not involve calculating the quantum force directly, but uses the wavefront to calculate the velocity field using mv=∇S, where S/ℏ is the argument of the wave function ψ. Additional numerical stability is gained by performing local gauge transformations to remove oscillatory components of the wave function. Finally, we use a dynamical Rayleigh–Ritz approach to derive ancillary equations-of-motion for the spatial derivatives of ρ, S, and v. The methodologies described herein dramatically improve the long time stability and accuracy of the quantum trajectory approach even in the presence of nodes. The method is applied to both barrier crossing and tunneling systems. We also compare our results to semiclassical based descriptions of barrier tunneling.
In this paper we compute quantum trajectories arising from Bohm’s causal description of quantum mechanics. Our computational methodology is based upon a finite-element moving least-squares method (MWLS) presented recently by Wyatt and co-workers [Lopreore and Wyatt, Phys. Rev. Lett. 82, 5190 (1999)]. This method treats the “particles” in the quantum Hamilton–Jacobi equation as Lagrangian fluid elements that carry the phase, S, and density, ρ, required to reconstruct the quantum wave function. Here, we compare results obtained via the MWLS procedure to exact results obtained either analytically or by numerical solution of the time-dependent Schrödinger equation. Two systems are considered: first, dynamics in a harmonic well and second, tunneling dynamics in a double well potential. In the case of tunneling in the double well potential, the quantum potential acts to lower the barrier, separating the right- and left-hand sides of the well, permitting trajectories to pass from one side to another. However, as probability density passes from one side to the other, the effective barrier begins to rise and eventually will segregate trajectories in one side from the other. We note that the MWLS trajectories exhibited long time stability in the purely harmonic cases. However, this stability was not evident in the barrier crossing dynamics. Comparisons to exact trajectories obtained via wave packet calculations indicate that the MWLS trajectories tend to underestimate the effects of constructive and destructive interference effects.
The quantum trajectory method (QTM) for time-dependent wave packet dynamics involves integration of the de Broglie–Bohm hydrodynamic equations for the evolving probability fluid [C. Lopreore and R. E. Wyatt, Phys. Rev. Lett. 82, 5190 (1999)]. The equations of motion for discretized elements of the probability fluid (particles) are integrated in the Lagrangian, moving with the fluid, picture. These fluid elements move under the influence of both the usual potential energy function and the quantum potential, which involves the curvature of the quantum amplitude. The quantum potential and the quantum force are evaluated using a moving weighted least squares algorithm. As a demonstration of applicability, the QTM is applied to a model collinear reaction with an activation barrier. The reaction probabilities are in good agreement with exact quantum results, even for a relatively small number of particles in the ensemble. The QTM accurately describes tunneling using only real valued trajectories. In addition to the reaction probability, plots are presented to show the probability density and the flux distributions at several time steps during the reaction.
A new method is proposed for computing the time evolution of quantum mechanical wave packets. Equations of motion for the real-valued functions C and S in the complex action S=C(r,t)+iS(r,t)/ℏ, with ψ(r,t)=exp(S), involve gradients and curvatures of C and S. In previous implementations of the hydrodynamic formulation, various time-consuming fitting techniques of limited accuracy were used to evaluate these derivatives around each fluid element in an evolving ensemble. In this study, equations of motion are developed for the spatial derivatives themselves and a small set of these are integrated along quantum trajectories concurrently with the equations for C and S. Significantly, quantum effects can be included at various orders of approximation, no spatial fitting is involved, there are no basis set expansions, and single quantum trajectories (rather than correlated ensembles) may be propagated, one at a time. Excellent results are obtained when the derivative propagation method is applied to anharmonic potentials involving barrier transmission.
The quantum hydrodynamic equations associated with the de Broglie–Bohm formulation of quantum mechanics are solved using a meshless method based on a moving least squares approach. An arbitrary Lagrangian–Eulerian frame of reference is used which significantly improves the accuracy and stability of the method when compared to an approach based on a purely Lagrangian frame of reference. A regridding algorithm is implemented which adds and deletes points when necessary in order to maintain accurate and stable calculations. It is shown that unitarity in the time evolution of the quantum wave packet is significantly improved by propagating using averaged fields. As nodes in the reflected wave packet start to form, the quantum potential and force become very large and numerical instabilities occur. By introducing artificial viscosity into the equations of motion, these instabilities can be avoided and the stable propagation of the wave packet for very long times becomes possible. Results are presented for the scattering of a wave packet from a repulsive Eckart barrier.
The de Broglie--Bohm causual (hydrodynamic) formulation of quantum mechanics is computationally implemented in the Lagrangian (moving with the fluid) viewpoint. The quantum potential and force are accurately evaluated with a moving weighted least squares algorithm. The quantum trajectory method is then applied to barrier tunneling on smooth potential surfaces. Analysis of the tunneling mechanism leads to a novel and accurate approximation: shortly after the wave packet is launched, completely neglect all quantum terms in the dynamical equations for motion along the tunneling coordinate.
The dynamics of a swarm of quantum trajectories is investigated for systems involving the interaction of an active mode (the subsystem) with an M-mode harmonic reservoir (the bath). Equations of motion for the position, velocity, and action function for elements of the probability fluid are integrated in the Lagrangian (moving with the fluid) picture of quantum hydrodynamics. These fluid elements are coupled through the Bohm quantum potential and as a result evolve as a correlated ensemble. Wave function synthesis along the trajectories permits an exact description of the quantum dynamics for the evolving probability fluid. The approach is fully quantum mechanical and does not involve classical or semiclassical approximations. Computational results are presented for three systems involving the interaction on an active mode with M=1, 10, and 15 bath modes. These results include configuration space trajectory evolution, flux analysis of the evolving ensemble, wave function synthesis along trajectories, and energy partitioning along specific trajectories. These results demonstrate the feasibility of using a small number of quantum trajectories to obtain accurate quantum results on some types of open quantum systems that are not amenable to standard quantum approaches involving basis set expansions or Eulerian space-fixed grids.