Perhaps because of the popularity that trajectory-based methodologies have always had in Chemistry and the important role they have played, Bohmian mechanics has been increasingly accepted within this community, particularly in those areas of the theoretical chemistry based on quantum mechanics, e.g., quantum chemistry, chemical physics, or physical chemistry. From a historical perspective, this evolution is remarkably interesting, particularly when the scarce applications of Madelung's former hydrodynamical formulation, dating back to the late 1960s and the 1970s, are compared with the many different applications available at present. As also happens with classical methodologies, Bohmian trajectories are essentially used to described and analyze the evolution of chemical systems, to design and implement new computational propagation techniques, or a combination of both. In the first case, Bohmian trajectories have the advantage that they avoid invoking typical quantum-classical correspondence to interpret the corresponding phenomenon or process, while in the second case quantum-mechanical effects appear by themselves, without the necessity to include artificially quantization conditions. Rather than providing an exhaustive revision and analysis of all these applications (excellent monographs on the issue are available in the literature for the interested reader, which can be consulted in the bibliography here supplied), this Chapter has been prepared in a way that it may serve the reader to acquire a general view (or impression) on how Bohmian mechanics has permeated the different traditional levels or pathways to approach molecular systems in Chemistry: electronic structure, molecular dynamics and statistical mechanics. This is done with the aid of some illustrative examples -- theoretical developments in some cases and numerical simulations in other cases.
Perhaps because of the popularity that trajectory-based methodologies have always had in Chemistry and the important role they have played, Bohmian mechanics has been increasingly accepted within this community, particularly in those areas of the theoretical chemistry based on quantum mechanics, e.g., quantum chemistry, chemical physics, or physical chemistry. From a historical perspective, this evolution is remarkably interesting, particularly when the scarce applications of Madelung's former hydrodynamical formulation, dating back to the late 1960s and the 1970s, are compared with the many different applications available at present. As also happens with classical methodologies, Bohmian trajectories are essentially used to described and analyze the evolution of chemical systems, to design and implement new computational propagation techniques, or a combination of both. In the first case, Bohmian trajectories have the advantage that they avoid invoking typical quantum-classical correspondence to interpret the corresponding phenomenon or process, while in the second case quantum-mechanical effects appear by themselves, without the necessity to include artificially quantization conditions. Rather than providing an exhaustive revision and analysis of all these applications (excellent monographs on the issue are available in the literature for the interested reader, which can be consulted in the bibliography here supplied), this Chapter has been prepared in a way that it may serve the reader to acquire a general view (or impression) on how Bohmian mechanics has permeated the different traditional levels or pathways to approach molecular systems in Chemistry: electronic structure, molecular dynamics and statistical mechanics. This is done with the aid of some illustrative examples -- theoretical developments in some cases and numerical simulations in other cases.
This chapter presents a brief account on both approaches, analytic and synthetic, within chemistry. It reviews the different levels at which molecular systems are traditionally studied. The chapter explores the Born–Oppenheimer approximation and then revisiting the methodologies available to deal with both electronic configuration and dynamics, distinguishing in this latter case between molecular dynamics for a few degree-of-freedom systems and statistical mechanics. It focuses on some fundamental aspects of Bohmian mechanics and describes some specific illustrations of the application of Bohmian mechanics to problems typical of the levels mentioned. Molecular systems typically include a rather large number of degrees of freedom, which makes unaffordable their direct study. In the wave model each atom is assumed to be a point-like, positively charged nucleus surrounded by an electronic cloud, which is associated with a certain orbital and represents the electron probability distribution in configuration space.
This chapter provides a comprehensive overview of the Bohmian formulation of quantummechanics. It starts with a historical review of the difficulties found by Louis de Broglie, David Bohm, and John S. Bell to convince the scientific community about the validity and utility of Bohmian mechanics. Then, a formal explanation of Bohmian mechanics for nonrelativistic, single-particle quantum systems is presented. The generalization to many-particle systems, where the exchange interaction and the spin play an important role, is also presented. After that, the measurement process in Bohmian mechanics is discussed. It is emphasized that Bohmian mechanics exactly reproduces the mean value and temporal and spatial correlations obtained from the standard, that is the Copenhagen or orthodox, formulation. The ontological characteristics of Bohmian mechanics provide a description of measurements as another type of interaction without the need for introducing the wave function collapse. Several solved problems are presented at the end of the chapter, giving additional mathematical support to some particular issues. A detailed description of computational algorithms to obtain Bohmian trajectories from the numerical solution of the Schro¨dinger or the Hamilton-Jacobi equations are presented in an appendix. The motivation of this chapter is twofold: first, as a didactic introduction to Bohmian formalism, which is used in the subsequent chapters, and second, as a self-contained summary for any newcomer interested in using Bohmian mechanics in his or her daily research activity.
In this chapter, a glimpse of the way how the concept of quantum trajectories has been used in different areas of quantum chemistry and chemical physics is provided. Putting aside ontological issues, Bohmian mechanics has been exploited within these fields with practical purposes, both analytical and computational. Analytically, although quantum trajectories provide the same information at a predictive level as standard quantum mechanics, they have the advantage that one can follow and describe the evolution of quantum systems by means of streamlines, whose results are less vague and more intuitive than standard wave packet simulations. On the other hand, computationally, Bohmian mechanics has been the source of a number of numerical algorithms devised as an alternative to other methods based on the wave function or the probability density. This will be seen throughout the analysis and discussion of different applications, which go from electronic structure to chemical dynamics, thus covering essentially the research spectrum of quantum chemistry and chemical physics. Furthermore, in the form of a final summary, we present a unifying scheme based on minimum principles, which allows us to connect electronic structurewith classical and quantum (Bohmian) chemical 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 quantum trajectory method in the hydrodynamical formulation of Madelung-Bohm-Takabayasi quantum mechanics is an example of showing the cognitive importance of scientific illustrations and metaphors in computational quantum chemistry and electrical engineering. The method involves several numerical schemes of solving a set of hydrodynamical equations of motion for probability density fluids, based on the propagation of those probability density trajectories. The quantum trajectory method gives rise to, for example, an authentic quantum electron transport theory of motion to, among others, classically-minded applied scientists who probably have less of a commitment to traditional quantum mechanics. They were not the usual audience of quantum mechanics and simply choose to use a non-Copenhagen type interpretation to their advantage. Thus, the metaphysical issues physicists had a trouble with are not the main concern of the scientists. With the advantages of a visual and illustrative trajectory, the quantum theory of motion by Bohm effectively bridges quantum and classical physics, especially, in the mesoscale domain. Without having an abrupt shift in actions and beliefs from the classical to the quantum world, scientists and engineers are able to enjoy human cognitive capacities extended into the quantum mechanical domain.
This chapter provides a comprehensive overview of the Bohmian formulation of quantum mechanics. It starts with a historical review of the difficulties found by Louis de Broglie, David Bohm, and John S. Bell to convince the scientific community about the validity and utility of Bohmian mechanics. Then, a formal explanation of Bohmian mechanics for nonrelativistic, single-particle quantum systems is presented. The generalization to many-particle systems, where the exchange interaction and the spin play an important role, is also presented. After that, the measurement process in Bohmian mechanics is discussed. It is emphasized that Bohmian mechanics exactly reproduces the mean value and temporal and spatial correlations obtained from the standard, that is the Copenhagen or orthodox, formulation. The ontological characteristics of Bohmian mechanics provide a description of measurements as another type of interaction without the need for introducing the wave function collapse. Several solved problems are presented at the end of the chapter, giving additional mathematical support to some particular issues. A detailed description of computational algorithms to obtain Bohmian trajectories from the numerical solution of the Schrodinger or the Hamilton-Jacobi equations are presented in an appendix. The motivation of this chapter is twofold: first, as a didactic introduction to Bohmian formalism, which is used in the subsequent chapters, and second, as a self-contained summary for any newcomer interested in using Bohmian mechanics in his or her daily research activity.