Abstract Despite the successful development of quantum chemistry, the deep breakdown between the conceptual basis of standard quantum mechanics and some implicit ontological assumptions of quantum chemistry is only rarely acknowledged. In fact, in the framework of standard quantum mechanics, quantum systems are not individual objects in the philosophical sense: they cannot be individualized by their positions in space and time and, as a consequence, they have no trajectories. By contrast, the basic magnitude in quantum chemistry is the electronic density, which is commonly interpreted in terms of the definite positions occupied by the individual electron in its motion around the nucleus. In the present paper, it will be argued that Bohmian Mechanics offers an ontological picture that is much closer to the quantum chemists’ way of conceiving their research field.
Abstract Despite the successful development of quantum chemistry, the deep breakdown between the conceptual basis of standard quantum mechanics and some implicit ontological assumptions of quantum chemistry is only rarely acknowledged. In fact, in the framework of standard quantum mechanics, quantum systems are not individual objects in the philosophical sense: they cannot be individualized by their positions in space and time and, as a consequence, they have no trajectories. By contrast, the basic magnitude in quantum chemistry is the electronic density, which is commonly interpreted in terms of the definite positions occupied by the individual electron in its motion around the nucleus. In the present paper, it will be argued that Bohmian Mechanics offers an ontological picture that is much closer to the quantum chemists’ way of conceiving their research field.
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.
Quantum chemistry is the branch of chemistry whose primary focus is the application of quantum mechanics to chemical systems at the molecular level. Precisely due to its peculiar position between chemistry and physics, in the last times it has begun to engage the interest of the philosophers of chemistry. Nevertheless, in this philosophical field, quantum chemistry has been studied mainly from a historical viewpoint or from a perspective interested on methodological issues. By contrast, the question that will guide this article is: what kind of ontic items are those studied by quantum chemistry? In order to develop the argumentation, first the relevance of the ontological questions will be addressed. Then, it will be considered in what measure the Born-Oppenheimer approximation and the quantum-chemistry concept of electron fit in the quantum theoretical context. Finally, some issues about what quantum chemistry refers to will be discussed.
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.
It is argued that in Bohmian mechanics the effective wave function of a subsystem of the universe does not encode the influences of other par-ticles on the subsystem. This suggests that the ontology of Bohmian mechanics does not consist only in Bohmian particles and their posi-tions. It is nonetheless pointed out that since the wave function in configuration space may represent the state of ergodic motion of non-Bohmian particles in three-dimensional space, the ontology of Bohmian mechanics may still consist only in particles. Bohmian mechanics, which is also called the de Broglie-Bohm theory, is a realistic alternative to standard quantum mechanics initially proposed by de Broglie (1928) and later developed by Bohm (1952). According to the theory, a complete realistic description of a quantum system is provided by the configuration defined by the positions of its particles together with its wave function. It has been a hot topic of debate how to interpret the wave function in the theory. Recently Esfeld et al (2013) further developed the nomological interpretation of the wave function, as suggested by Dürr, Goldstein and Zangh̀ı (1997), Goldstein and Teufel (2001) and Goldstein and Zangh̀ı (2012). They argued that the ontology of Bohmian mechanics consists only in Bohmian particles and their positions, and in particular, the effective wave function of a subsystem of the universe encodes the influences of other particles in the universe on the subsystem. In this note, we will argue that this interesting view may be problematic. The Bohmian law of motion is expressed by two equations, a guiding equation for the configuration of particles in three-dimensional space and the Schrödinger equation, describing the time evolution of the wave function, which enters the guiding equation. The law can be formulated as follows: dQ(t) dt = vΨ(t)(Q(t)). (1)
The ontological interpretation of Bohmian quantum mechanics, through a particle's visual trajectory of motion, reconstitutes realism and determinism (and thus causality) in a quantum system. There also exists a similar but distinctive class of interpretation under Bohmian quantum mechanics, called the hydrodynamical interpretation. Here, the trajectories of the probability fluid flow play a significant computational role. The flow of the probability density visually helps chemists and engineers to solve the corresponding quantum hydrodynamical equations of motion. This particular computational scheme for the numerical solutions is called ‘the quantum trajectory method.' The success of the quantum trajectory method demonstrates the power of visual illustrations and metaphors in representing and analyzing quantum systems.
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.