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The Journal of Chemical Physics

Dissociation dynamics from a de Broglie–Bohm perspective

Zhen Wang, George R. Darling, S. Holloway

Published Dec 8, 2001• 28 citations
Publisher

Abstract

Within the framework of Bohm’s reformulation of quantum physics we revisit the activated dissociation of hydrogen molecules at metal surfaces. The quantum-mechanical force, which accounts for most of quantum effects in the method, and is caused by nonlocal, topographical properties of the wave function, is computed using time-dependent wave packets obtained using conventional, spectral methods. Driven by a combination of the classical force together with the quantum force, trajectories carrying probability density either succeed in overcoming the barrier for dissociation or are scattered back into the gas phase. The Bohmian picture for the dissociation process has enabled us to develop a novel mechanism to account for vibrationally enhanced molecular dissociation. This is relevant to the recently observed promotion of dissociation of very highly vibrationally excited NO molecules at Cu surfaces.

DOI
10.1063/1.1415450

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Within the framework of Bohm’s reformulation of quantum physics we revisit the activated dissociation of hydrogen molecules at metal surfaces. The quantum-mechanical force, which accounts for most of quantum effects in the method, and is caused by nonlocal, topographical properties of the wave function, is computed using time-dependent wave packets obtained using conventional, spectral methods. Driven by a combination of the classical force together with the quantum force, trajectories carrying probability density either succeed in overcoming the barrier for dissociation or are scattered back into the gas phase. The Bohmian picture for the dissociation process has enabled us to develop a novel mechanism to account for vibrationally enhanced molecular dissociation. This is relevant to the recently observed promotion of dissociation of very highly vibrationally excited NO molecules at Cu surfaces.
The exact factorization of an electron-nuclear wave function [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)] allows us to define the rigorous nuclear time-dependent Schr\"odinger equation (TDSE) with a time-dependent potential-energy surface (TDPES) that fully accounts for the coupling to the electronic motion and drives the nuclear wave-packet dynamics. Here, we study whether the propagation of multiple classical trajectories can reproduce the quantum nuclear motion in strong-field processes when their motions are governed by the quantum Hamilton-Jacobi equation derived by applying Bohmian mechanics to this exact nuclear TDSE. We demonstrate that multiple classical trajectories propagated by the force from the gradient of the exact TDPES plus the Bohmian quantum potential can reproduce the strong-field dissociation dynamics of a one-dimensional model of the H2+{{\mathrm{H}}_{2}}^{+}H2​+ molecule. Our results show that the force from the Bohmian quantum potential plays a non-negligible role in yielding quantum nuclear dynamics in the strong-field process studied here, where ionization and/or splitting of nuclear probability density occurs.
Bohmian mechanics is endowed with an ontological package that supposedly allows to solve the main interpretational problems of quantum mechanics. We are concerned in this work by the emergence of classicality from the quantum mechanical substrate. We will argue that although being superficially attractive, the de Broglie-Bohm interpretation does not shed new light on the quantum-to-classical transition. This is due to nature of the dynamical law of Bohmian mechanics by which the particles follow the streamlines of the probability flow. As a consequence, Bohmian trajectories can be highly non-classical even when the wavefunction propagates along classical trajectories, as happens in semiclassical systems. In order to account for classical dynamics, Bohmian mechanics needs non-spreading and non-interfering wave packets: this is achieved for practical purposes by having recourse to decoherence and dense measurements. However one then faces the usual fundamental problems associated with the meaning of reduced density matrices. Moreover the specific assets of the de Broglie-Bohm interpretation – in particular the existence of point-like particles pursuing well-defined trajectories – would play no role in accounting for the emergence of classical dynamics.
Bohm theory is a formulation of Quantum Mechanics that characterises the state of a quantum system according to both the wave function, as in the conventional formulation, and the coordinates (positions) of all the particles that evolve in time drawing quantum continuous trajectories. Furthermore, a statistical ensemble of all the possible trajectories, raising from the impossibility to know the initial position of all the particles, establishes the exact correspondence with the traditional Quantum Mechanics. From a computational point of view, Bohm theory has found many applications in Chemical Physics especially to develop new methodologies for solving the Schrödinger equation and to address semi-classical approximations of Quantum Mechanics. From a theoretical point of view, the most appealing feature of Bohm theory is its capability to supply a conceptual map between the quantum formalism and our representation of what a chemical system is. Chemical systems are composed of molecules, but the same idea of molecule requires a specific arrangement in the space of particles, i.e., the nuclei of the atoms. The statistical description of conventional Quantum Mechanics on the basis of wave function alone is insufficient to establish a clear correspondence with such a picture of molecules. Indeed, chemists employ usually Classical Mechanics in order to overcome this drawback of the standard quantum theory. On the other hand, if the particles position is included in the quantum formalism, as Bohm theory does, the map can be defined in a self-consistent way. In other words, Bohm theory appears to be the suitable quantum framework to represent molecules and their motion. The chemical representation of molecular systems finds a natural correspondence with a single Bohm trajectory, since it is always implicitly assumed that molecular components have specific spatial position independently of our knowledge about it. Consequently, we develop a quantum method whose fundamental assumption is that a single Bohm trajectory, i.e., a quantum molecular trajectory, describes the molecular systems and the molecular motion correctly. First of all, we examine the correspondence between a single Bohm trajectory and the conventional Quantum Mechanics, without using the ensemble of trajectories. We verify that such a correspondence exists through numerical simulations and we prove formally that the statistical properties of a single Bohm trajectory explain the probabilistic description of Quantum Mechanics. Once the consistency of this original approach has been established, we investigate the predicted properties. For instance, we take into account the constants of motion (such as the energy) corresponding to the time evolution of the coordinates and the behaviour of simple chemical systems, e.g., the vibrational motion of single molecules interacting with a resonant field. In this way, unexpected features of the molecular motion are found. Secondly, we tackle the challenge of describing many components systems (like the chemical systems in ordinary conditions). As a matter of fact, the computation of the Bohm trajectory and of the wave function is extremely demanding. However, the statistical properties of the Bohm trajectory allow the derivation of stochastic theories for examining the dynamics of open quantum systems, i.e., few molecules (or few degrees of freedom) interacting with their environment (the other molecules). One of the developed stochastic methods correlates the dynamics of the reduced density matrix, for the degrees of freedom of interest, to the evolution of the corresponding Bohm coordinates. In other words, the Bohm equation, determining the set of all the particles velocities according to the full wave function, is replaced with a stochastic one that approximates the velocity of a subset of coordinates according to the reduced density matrix. In such a way, the quantum fluctuations induced by the environment are taken into account. The advantage of this method concerns its capability of describing quantum systems, including open quantum systems, in terms of a quantum trajectory. This could allow the understanding of the molecular motion during a spectroscopical experiment. The possibility of investigating reactive systems, such as conformational changes, is particularly interesting. As a matter of fact, chemical reactions can be completely characterised only through the particles motion and we define the suit- able quantum methodology providing a self-consistent description of the molecular motion.
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.
Non-relativistic de Broglie–Bohm theory describes particles moving under the guidance of the wave function. In de Broglieʼs original formulation, the particle dynamics is given by a first-order differential equation. In Bohmʼs reformulation, it is given by Newtonʼs law of motion with an extra potential that depends on the wave function—the quantum potential—together with a constraint on the possible velocities. It was recently argued, mainly by numerical simulations, that relaxing this velocity constraint leads to a physically untenable theory. We provide further evidence for this by showing that for various wave functions the particles tend to escape the wave packet. In particular, we show that for a central classical potential and bound energy eigenstates the particle motion is often unbounded. This work seems particularly relevant for ways of simulating wave function evolution based on Bohmʼs formulation of the de Broglie–Bohm theory. Namely, the simulations may become unstable due to deviations from the velocity constraint.
The de Broglie-Bohm causal interpretation of quantum mechanics is discussed, and applied to the hydrogen atom in several contexts. Prominent critiques of the causal program are noted and responses are given; it is argued that the de Broglie-Bohm theory is of notable interest to physics. Using the causal theory, electron trajectories are found for the conventional Schrödinger, Pauli and Dirac hydrogen eigenstates. In the Schrödinger case, an additional term is used to account for the spin; this term was not present in the original formulation of the theory but is necessary for the theory to be embedded in a relativistic formulation. In the Schrödinger, Pauli and Dirac cases, the eigenstate trajectories are shown to be circular, with electron motion revolving around the z-axis. Electron trajectories are also found for the 1s-2p0 transition problem under the Schrödinger equation; it is shown that the transition can be characterized by a comparison of the trajectory to the relevant eigenstate trajectories. The structures of the computed trajectories are relevant to the question of the possible evolution of a quantum distribution towards the standard quantum distribution (quantum equilibrium); this process is known as quantum relaxation. The transition problem is generalized to include all possible transitions in hydrogen stimulated by semi-classical radiation, and all of the trajectories found are examined in light of their implications for the evolution of the distribution to the standard distribution. Several promising avenues for future research are discussed.