Despite the quantum nature of molecules, classical mechanics is often employed to describe molecular motions that play a fundamental role in a wide range of phenomena including chemical reactions. This is due to the need of assigning well-defined positions to the atomic nuclei during the time evolution of the system in order to describe unambiguously the molecular motions, whereas quantum mechanics provides information on probabilistic nature only. One would like to employ a quantum molecular trajectory that defines rigorously the instantaneous nuclear positions and, simultaneously, guarantees the conservation of all quantum mechanics predictions unlike the classical trajectory. We argue that such a quantum molecular trajectory can be formally defined and we prove that it corresponds to a single Bohm trajectory. Our analysis establishes a clear correspondence between the statistical properties of the trajectory and the quantum expectation values. The obvious and undeniable benefit is that of dealing with a quantum methodology fully characterizing the molecular motions without any reference to classical mechanics.
Despite the quantum nature of molecules, classical mechanics is often employed to describe molecular motions that play a fundamental role in a wide range of phenomena including chemical reactions. This is due to the need of assigning well-defined positions to the atomic nuclei during the time evolution of the system in order to describe unambiguously the molecular motions, whereas quantum mechanics provides information on probabilistic nature only. One would like to employ a quantum molecular trajectory that defines rigorously the instantaneous nuclear positions and, simultaneously, guarantees the conservation of all quantum mechanics predictions unlike the classical trajectory. We argue that such a quantum molecular trajectory can be formally defined and we prove that it corresponds to a single Bohm trajectory. Our analysis establishes a clear correspondence between the statistical properties of the trajectory and the quantum expectation values. The obvious and undeniable benefit is that of dealing with a quantum methodology fully characterizing the molecular motions without any reference to classical mechanics.
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.
Molecular systems are quantum systems, but the complete characterization of molecular motions within a fully quantum framework might appear to be an unfeasible task because it would require that the actual nuclear positions are established at any time. One would like to use a quantum molecular trajectory that defines the instantaneous nuclear positions and satisfies the predictions of quantum mechanics in terms of its statistical properties. Even though it can be proven that the single Bohm trajectory provides a representation of the quantum molecular trajectory, this solves the issue only on a theoretical ground: exact solutions of the Schrödinger-Bohm dynamical system are extremely computationally demanding. Therefore, we derive a stochastic equation of Smoluchowski type from the Schrödinger-Bohm dynamics, through projection operator techniques, in order to characterize the molecular motions of open quantum systems. The main quantum features of the motions emerge from the equilibrium distribution, i.e., the wave function's squared modulus integrated on the environment degrees of freedom. Furthermore, we verify the accuracy of the stochastic equation by comparing its predictions with those of the deterministic dynamics for a model system of six interacting harmonic oscillators. The indisputable advantage of this full quantum mechanical approach is that of representing the molecular dynamics, which controls important phenomena like vibrational relaxation, conformational transitions and activated processes, in a self consistent way and at the low computational cost of solving simple stochastic equations.
The quantum molecular trajectory is the deterministic trajectory, arising from the Bohm theory, that describes the instantaneous positions of the nuclei of molecules by assuring the agreement with the predictions of quantum mechanics. Therefore, it provides the suitable framework for representing the geometry and the motions of molecules without neglecting their quantum nature. However, the quantum molecular trajectory is extremely demanding from the computational point of view, and this strongly limits its applications. To overcome such a drawback, we derive a stochastic representation of the quantum molecular trajectory, through projection operator techniques, for the degrees of freedom of an open quantum system. The resulting Fokker-Planck operator is parametrically dependent upon the reduced density matrix of the open system. Because of the pilot role played by the reduced density matrix, this stochastic approach is able to represent accurately the main features of the open system motions both at equilibrium and out of equilibrium with the environment. To verify this procedure, the predictions of the stochastic and deterministic representation are compared for a model system of six interacting harmonic oscillators, where one oscillator is taken as the open quantum system of interest. The undeniable advantage of the stochastic approach is that of providing a simplified and self-contained representation of the dynamics of the open system coordinates. Furthermore, it can be employed to study the out of equilibrium dynamics and the relaxation of quantum molecular motions during photoinduced processes, like photoinduced conformational changes and proton transfers.
Chemical dynamics, in principle, should be understood by solving the time-dependent Schrödinger equation for a molecular system, describing motion of the nuclei and electrons. However, the computational efforts to solve this partial second-order differential equation scales exponentially with the system size, which prevents us from getting exact numerical solutions for systems larger than 4-5 atoms. Thus, approximations simplifying the picture are necessary. The so-called Born-Oppenheimer approximation, separating motion of the electrons and nuclei is the central one: solution to the electronic Schrödinger equation defines the potential energy surface on which the nuclear motion unfolds, and there are standard quantum chemistry software packages for solving the electronic Schrödinger equation. For the nuclear Schrödinger equation, however, there are no widely applicable quantum-mechanical approaches, and most simulations are performed using classical Newtonian mechanics which is often adequate due to large nuclear masses. However, the nuclear quantum effects are significant for chemical processes involving light nuclei at low energies, and including these effects into simulation, even approximately, is highly desirable. In this dissertation, an approximate methodology of including quantum-mechanical effects within the quantum trajectory or the de Broglie-Bohm formulation of the Schrödinger equations is developed. Use of the trajectory framework makes the approach scalable to hundreds of degrees of freedom. The methodology is applied to study high-dimensional systems (solid He4 and others) relevant to chemistry.
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.
The application of modern quantum chemical methods to the simulation of chemical reactions makes it obvious that the Copenhagen picture of quantum mechanics cannot be maintained. In ab-initio molecular dynamics methods, any kind of matter is described by applying the Schrödinger equation to the electronic structure and using classical Newton dynamics for the motion of the atomic nuclei. By lots of calculations on this basis, it has become obvious that this concept is superior to a quantum chemical description of nuclear motion. The nuclei move according to Newton's laws in a perfectly local and deterministic way while the surrounding electronic cloud determines bonding and antibonding interactions between the atoms. The resulting theory is a deterministic formulation of quantum mechanics which is free from paradoxa and is able to explain complex phenomena like photochemistry. An obvious consequence is that molecules like ammonia can have a permanent dipole moment in spectroscopic measurements, while consistent application of traditional quantum mechanics predicts a higher symmetry as is outlined in the paper.