The Madelung-de Broglie-Bohm formulation of the Schrödinger equation casts the time-evolution of a wave function as dynamics of an ensemble of quantum, or Bohmian, trajectories, interacting via the nonlocal quantum potential. This trajectory perspective gives insight into the quantumness (or classicality) of a given system due to clear partitioning of the energy into classical and quantum components. Here, we propose a system-independent measure of the quantumness of dynamics, based on the energy time-change, referred to as "quantum power". This measure is local in the coordinate space. Based on applications to model chemical systems, we argue that during the transition from the quantum to classical regime, defined as compression of quantization, the quantum features in dynamics do not "disappear" but are pushed forward in time. This feature may be used to gauge the validity of the semiclassical and other approximate dynamics approaches in applications to anharmonic systems.
The Madelung-de Broglie-Bohm formulation of the Schrödinger equation casts the time-evolution of a wave function as dynamics of an ensemble of quantum, or Bohmian, trajectories, interacting via the nonlocal quantum potential. This trajectory perspective gives insight into the quantumness (or classicality) of a given system due to clear partitioning of the energy into classical and quantum components. Here, we propose a system-independent measure of the quantumness of dynamics, based on the energy time-change, referred to as "quantum power". This measure is local in the coordinate space. Based on applications to model chemical systems, we argue that during the transition from the quantum to classical regime, defined as compression of quantization, the quantum features in dynamics do not "disappear" but are pushed forward in time. This feature may be used to gauge the validity of the semiclassical and other approximate dynamics approaches in applications to anharmonic systems.
The quantum nature of nuclei often affects molecular structure and properties, which are associated with the motion of protons and other light nuclei at low temperature. However, incorporation of the nuclear quantum effects into theoretical studies of large molecular systems is an outstanding challenge in theoretical chemistry. In this paper, the de Broglie-Bohm formulation of the time-dependent Schrödinger equation is used as a framework for the development of approximate quantum corrections to the dynamics of a trajectory ensemble, representing a time-dependent wave function. Specifically, the trajectory-centered local Least Square Fit (L-LSF) to the trajectory attributes is introduced, formally analyzed and illustrated on model potentials, typically used to benchmark approximate and semiclassical dynamics methods. The L-LSF method improves the dynamics accuracy, compared to the globally defined approximations, developed previously, and is shown to converge to the exact (generally impractical for large systems) limit of quantum dynamics.
A classical limit of quantum dynamics can be defined by compensation of the quantum potential in the time-dependent Schrödinger equation. The quantum potential is a non-local quantity, defined in the trajectory-based form of the Schrödinger equation, due to Madelung, de Broglie, and Bohm, which formally generates the quantum-mechanical features in dynamics. Selective inclusion of the quantum potential for the degrees of freedom deemed "quantum," defines a hybrid quantum/classical dynamics, appropriate for molecular systems comprised of light and heavy nuclei. The wavefunction is associated with all of the nuclei, and the Ehrenfest, or mean-field, averaging of the force acting on the classical degrees of freedom, typical of the mixed quantum/classical methods, is avoided. The hybrid approach is used to examine evolution of light/heavy systems in the harmonic and double-well potentials, using conventional grid-based and approximate quantum-trajectory time propagation. The approximate quantum force is defined on spatial domains, which removes unphysical coupling of the wavefunction fragments corresponding to distinct classical channels or configurations. The quantum potential, associated with the quantum particle, generates forces acting on both quantum and classical particles to describe the backreaction.
The quantum trajectories in the de Broglie-Bohm formulation of quantum mechanics depend on an additional quantum potential derived from the full wave solution of Schrödinger's equation. The task of supplying collectively all the correct quantum results strongly alters the characteristics of the corresponding classical trajectories, which underlie semiclassical approximations to the evolving wave function. Both classical and quantum trajectories are here considered to be conservative with no influence of an external environment, even though this is the source of eventual classicality in quantum systems, that is, decoherence. The concept of integrability, closely correspondent in classical and quantum mechanics, is not preserved by the quantum trajectories. General systems, in which classical chaotic motion participates, are much harder to treat semiclassically, but quantum trajectories can be chaotic even for integrable systems. This discrepancy between the character of classical and quantum trajectories in the de Broglie-Bohm interpretation does not clarify the singular classical-quantum transition.
The approach of defining quantum corrections on nuclear dynamics of molecular systems incorporated approximately into selected degrees of freedom, is described. The approach is based on the Madelung-de-Broglie-Bohm formulation of time-dependent quantum mechanics which represents a wavefunction in terms of an ensemble of trajectories. The trajectories follow classical laws of motion except that the quantum potential, dependent on the wavefunction amplitude and its derivatives, is added to the external, classical potential. In this framework the quantum potential, determined approximately for practical reasons, is included only into the "quantum" degrees of freedom describing light particles such as protons, while neglecting with the quantum force for the heavy, nearly classical nuclei. The entire system comprised of light and heavy particles is described by a single wavefunction of full dimensionality. The coordinate space of heavy particles is divided into spatial domains or subspaces. The quantum force acting on the light particles is determined for each domain of similar configurations of the heavy nuclei. This approach effectively introduces parametric dependence of the reduced dimensionality quantum force, on classical degrees of freedom. This strategy improves accuracy of the quantum force and does not restrict interaction between the domains. The concept is illustrated for two-dimensional scattering systems, where the quantum force is required to reproduce vibrational energy of the quantum degree of freedom.
It is shown that for any given quantum system evolving unitarily with the Hamiltonian, H^=p^2/(2m)+U(q), [bold letters denote D-dimensional (D⩾3) vectors] and with a sufficiently smooth potential U(q), there exits a classical ensemble with the Hamilton function, $\mathrsfs{H} ({\bf p}, {\bf q}) = {\bf p}^2/(2m) + U^{(\infty)} ({\bf q})$, where the potential U(∞)(q) coincides with U(q) for almost all q (i.e., U(∞) can be different from U only on a measure zero set), such that the square modulus of the wave function in the coordinate (momentum) representation approximately equals the coordinate (momentum) distribution of the classical ensemble within an arbitrary given accuracy. Furthermore, the trajectories of this classical ensemble, generally speaking, need not coincide with the trajectories obtained from de Broglie--Bohmian mechanics. Consequences of this result are discussed.
The introduction of nonlinearities in the Schrödinger equation has been considered in the literature as an effective manner to describe the action of external environments or mean fields. Here, in particular, we explore the nonlinear effects induced by subtracting a term proportional to Bohm’s quantum potential to the usual (linear) Schrödinger equation, which generates the so-called “classical” Schrödinger equation. Although a simple nonlinear transformation allows us to recover the well-known classical Hamilton–Jacobi equation, by combining a series of analytical results (in the limiting cases) and simulations (whenever the analytical treatment is unaffordable), we find an analytical explanation to why the dynamics in the nonlinear “classical” regime is still strongly nonclassical. This is even more evident by establishing a one-to-one comparison between the Bohmian trajectories associated with the corresponding wave function and the classical trajectories that one should obtain. Based on these observations, it is clear that the transition to a fully classical regime requires extra conditions in order to remove any trace of coherence, which is the truly distinctive trait of quantum mechanics. This behavior is investigated in three paradigmatic cases, namely, the dispersion of a free propagating localized particle, the harmonic oscillator, and a simplified version of Young’s two-slit experiment.