Transcending its origin in the debate on the interpretation of quantum theory, the continuous deterministic trajectory has proved a potent tool in computational quantum mechanics (an excellent introduction to numerical trajectory techniques is provided by Wyatt’s text [1]). It is straightforward to develop a method to derive the timedependent Schrödinger equation from a single-valued continuum of spacetime trajectories, and supply a corresponding exact formula for the wavefunction [2].Anatural language for this theory of evolution is offered by the hydrodynamic analogy, in which wave mechanics corresponds to the Eulerian picture (as shown by Madelung [3]) and the trajectory theory to the Lagrangian picture. The Lagrangian model for the quantum fluid may be developed from a variational principle involving a specific interaction potential (the quantum internal potential energy), and the Euler-Lagrange equations imply a nonlinear partial differential equation to calculate the trajectories of the fluid particles as functions of their initial coordinates and the initial wavefunction. The latter supplies two sets of data to the particle model: the initial density (via the amplitude) and the initial velocity (via the phase). The time-dependent wavefunction is then computed via the standard map between the Lagrangian coordinates and the Eulerian fields.
Transcending its origin in the debate on the interpretation of quantum theory, the continuous deterministic trajectory has proved a potent tool in computational quantum mechanics (an excellent introduction to numerical trajectory techniques is provided by Wyatt’s text [1]). It is straightforward to develop a method to derive the timedependent Schrödinger equation from a single-valued continuum of spacetime trajectories, and supply a corresponding exact formula for the wavefunction [2].Anatural language for this theory of evolution is offered by the hydrodynamic analogy, in which wave mechanics corresponds to the Eulerian picture (as shown by Madelung [3]) and the trajectory theory to the Lagrangian picture. The Lagrangian model for the quantum fluid may be developed from a variational principle involving a specific interaction potential (the quantum internal potential energy), and the Euler-Lagrange equations imply a nonlinear partial differential equation to calculate the trajectories of the fluid particles as functions of their initial coordinates and the initial wavefunction. The latter supplies two sets of data to the particle model: the initial density (via the amplitude) and the initial velocity (via the phase). The time-dependent wavefunction is then computed via the standard map between the Lagrangian coordinates and the Eulerian fields.
We discuss the particle method in quantum mechanics which provides an exact scheme to calculate the time-dependent wavefunction from a single-valued continuum of trajectories where two spacetime points are linked by at most a single orbit. A natural language for the theory is offered by the hydrodynamic analogy, in which wave mechanics corresponds to the Eulerian picture and the particle theory to the Lagrangian picture. The Lagrangian model for the quantum fluid may be developed from a variational principle. The Euler-Lagrange equations imply a fourth-order nonlinear partial differential equation to calculate the trajectories of the fluid particles as functions of their initial coordinates using as input the initial wavefunction. The admissible solutions are those consistent with quasi-potential flow. The effect of the superposition principle is represented via a nonclassical force on each particle. The wavefunction is computed via the standard map between the Lagrangian coordinates and the Eulerian fields, which provides the analogue in this model of Huygens principle in wave mechanics. The method is illustrated by calculating the time-dependence of a free Gaussian wavefunction. The Eulerian and Lagrangian pictures are complementary descriptions of a quantum process in that they have associated Hamiltonian formulations that are connected by a canonical transformation. The de Broglie-Bohm interpretation, which employs the same set of trajectories, should not be conflated with the Lagrangian version of the hydrodynamic interpretation. The theory implies that the mathematical results of the de Broglie-Bohm model may be regarded as statements about quantum mechanics itself rather than about its interpretation.
The quantum trajectory method (QTM) is extended to the dynamics of electronic nonadiabiatic collisions. Equations of motion are first derived for the probability density, velocity, and action function for wave packets moving on each of the coupled electronic potential surfaces. These discretized equations are solved in the Lagrangian (moving with the fluid) picture to give the trajectory dynamics of fluid elements evolving on each potential surface. This trajectory method is fully quantum mechanical and does not involve “trajectory surface hopping.” The method is applied to nonadiabiatic collision models involving two coupled electronic states. The quantum trajectory results are in excellent agreement with solutions computed (using space-fixed grid methods) directly from the time-dependent Schrödinger equation.
The study of many problems in quantum mechanics is based on finding the solution to the time-dependent Schrodinger equation which describes the dynamics of quantum-mechanical systems composed of a particle of mass m moving in a potential V. Based on the hydrodynamic interpretation of quantum mechanics by Bohm (1952), an unstructured grid approach, the quantum trajectory method (QTM) was developed by Lopreore and Wyatt (1999). Derivatives needed for updating the equations of motion are obtained using curve-fitting by a moving weighted least squares algorithm, and analytically differentiating the least squares curves. The calculations involve computationally-intensive parallel loops with nonuniform iterate execution times
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.
Recently, in an effort to solve more realistic problems in quantum dynamics, much attention has been directed into numerically integrating the quantum hydrodynamic equations of motions (QHEM), as opposed to directly solving the time-dependent Schrödinger equation (TDSE). Such efforts have been provoked by the many numerical drawbacks encountered when solving the TDSE on a fixed-grid. In this dissertation, one trajectory method for integrating the QHEM is reviewed, and two novel trajectories methods are described. The first of these, the quantum trajectory method (QTM), was introduced in 1999 and has been used to solve many problems in quantum dynamics since then. However, severe numerical problems are encountered when this method is applied to problems that form wave function nodes. To get around this problem, new methods for numerically integrating the QHEM are needed. In the first novel method described, the arbitrary Lagrangian-Eulerian (ALE) method, particle trajectories are governed by a predetermined equation of motion that is user-supplied. The ALE method remedies inflation and compression problems encountered in the pure Lagrangian QTM. In the second new method discussed, the derivative propagating method (DPM), single quantum trajectories can be calculated one at a time, as opposed to the ensemble propagation of the QTM and ALE method. Using these two methods, new solutions to the QHEM are obtained where the QTM fails. In addition to solving the QHEM, the DPM is also used to solve the classical Klein-Kramers equation in this dissertation. This equation governs the Markovian phase space evolution of a system coupled to an environment such as a heat bath. This marks the first time single trajectories have been used to solve both the QHEM and the Klein-Kramers equations.
A generalized Euler equation of fluid dynamics is derived for describing many-body states of quantum mechanics. The Eulerian Eq. can be viewed as representing the interaction of two substates, where each substate has its own velocity and pressure fields. These field quantities are given by maps of the wavefunction. For one-body systems, the Eulerian Eq. can model either a fluid or particle description of quantum states. The generalized Euler Eq. is shown to be the gradient of an equation representing the total-energy of the two substates, having two energy fields. This total-energy Eq. is a generalization of the Bernoulli Eq. of fluid dynamics. The total-energy Eq., along with a continuity-equation, is equivalent to the time-dependent Schroedinger Eq. An equation is also derived that is equivalent to the main equation of Bohmian mechanics with additional identifications: The quantum potential of Bohmian mechanics is given as a sum of a kinetic energy and pressure fields. Also, the time derivative of the wavefunction phase is replaced by an energy field. In the formalism, field quantities are identified from their placement in equations of classical mechanics and separately, by definitions that involve the wavefunction and operators of quantum mechanics. This approach yields, unintended, and unknown energy and pressure fields. These fields, however, are shown to satisfy a continuity Eq., an equation that is equivalent to the other equation of Bohmian mechanics. It is also demonstrated that energy conservation holds for both of these energy fields, if the wavefunction is a linear-combination of eigenvectors, where the eigenvectors can be nondegenerate. A detailed investigation is given on the possible behavior, or source, of an electron that has one of the velocity fields. Alternate formulae for this velocity fields are also considered.