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International Journal of Quantum Chemistry

Quantum molecular dynamics

Burke Ritchie

Published Oct 13, 2009• 10 citations
Publisher

Abstract

Abstract Electron or ion dynamics are treated using spin‐dependent quantum trajectories. These trajectories are inferred from the Dirac current, which contributes Schroedinger's current and additional spin‐dependent terms, all of which are of order c0 in the nonrelativistic regime of particle velocity, where c is the speed of light. The many‐body problem is treated precisely as in classical dynamics. Each electron or ion has its own equation of motion, which is the time‐dependent Dirac or the time‐dependent Schroedinger equation in the relativistic or nonrelativistic regime of particle velocity, respectively. As an example the theory is applied to the electronic structure of the helium atom, in which two electrons with opposite spin states are shown to correlate such that their quantum trajectories keep them on average on opposite sides of the nucleus. As the theory is time dependent, excited states are also generated. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

DOI
10.1002/qua.22371

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Abstract Electron or ion dynamics are treated using spin‐dependent quantum trajectories. These trajectories are inferred from the Dirac current, which contributes Schroedinger's current and additional spin‐dependent terms, all of which are of order c0 in the nonrelativistic regime of particle velocity, where c is the speed of light. The many‐body problem is treated precisely as in classical dynamics. Each electron or ion has its own equation of motion, which is the time‐dependent Dirac or the time‐dependent Schroedinger equation in the relativistic or nonrelativistic regime of particle velocity, respectively. As an example the theory is applied to the electronic structure of the helium atom, in which two electrons with opposite spin states are shown to correlate such that their quantum trajectories keep them on average on opposite sides of the nucleus. As the theory is time dependent, excited states are also generated. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2011
The relationship between the spin of an individual electron and Fermi‐Dirac statistics (FDS), which is obeyed by electrons in the aggregate, is elucidated. The relationship depends on the use of spin‐dependent quantum trajectories (SDQT) to evaluate Coulomb’s law between any two electrons as an instantaneous interaction in space and time rather than as a quantum‐mean interaction in the form of screening and exchange potentials. Hence FDS depends in an ab initio sense on the inference of SDQT from Dirac’s equation, which provides for relativistic Lorentz invariance and a permanent magnetic moment (or spin) in the electron’s equation of motion. Schroedinger’s time‐dependent equation can be used to evaluate the SDQT in the nonrelativistic regime of electron velocity. Remarkably FDS is a relativistic property of an ensemble of electron, even though it is of order c 0 in the nonrelativistic limit, in agreement with experimental observation. Finally it is shown that covalent versus separated‐atoms limits can be characterized by the SDQT. As an example of the use of SDQT in a canonical structure problem, the energies of the 1 Σ g and 3 Σ u states of H 2 are calculated and compared with the accurate variational energies of Kolos and Wolniewitz.
Abstract The time‐dependent Schrödinger equation can be rewritten so that its interpretation is no longer probabilistic. Two well‐known and related reformulations are Bohmian mechanics and quantum hydrodynamics. In these formulations, quantum particles follow real, deterministic trajectories influenced by a quantum force. Generally, trajectory methods are not applied to electronic structure calculations as they predict that the electrons in a ground‐state, real, molecular wavefunction are motionless. However, a spin‐dependent momentum can be recovered from the nonrelativistic limit of the Dirac equation. Therefore, we developed new, spin‐dependent equations of motion for the quantum hydrodynamics of electrons in molecular orbitals. The equations are based on a Lagrange multiplier, which constrains each electron to an isosurface of its molecular orbital, as required by the spin‐dependent momentum. Both the momentum and the Lagrange multiplier provide a unique perspective on the properties of electrons in molecules.
Abstract We show that the quantum central‐force problems can be modeled and solved exactly by quantum Hamilton–Jacobi formulation, from which the quantum operators L^\hat{L}L^ z, L^\hat{L}L^ 2, and H^\hat{H}H^ can be derived without using the quantization principle p → (ℏ\hbarℏ /i)∂/∂x. Quantum conservation laws expressed by the Poisson bracket show that the eigenvalues of these quantum operators are just equal to the constants of motion along the eigen‐trajectories defined in a complex domain. The shell structure observed in bound systems, such as the hydrogen atom, is found to stem from the structure of the quantum potential, by which the quantum forces acting on the electron can be uniquely determined, the stability of atomic configuration can be justified, and the quantum trajectories of the electron can be obtained by integrating the related quantum Lagrange equations. On solving the quantum equations of motion, the solution of the Schrödinger equation serves as the first integration of the second‐order quantum Lagrange equations. The stable equilibrium points of the derived first‐order nonlinear quantum dynamics are shown to be identical to the positions with maximum probability predicted by standard quantum mechanics. The internal mechanism of how the quantum dynamics evolve continuously to classical dynamics and of how the quantum conservation laws transit continuously to the classical conservation laws as n → ∞ are analyzed in detail. The construction of the quantum scattering trajectory by searching for an unbound solution for the Schrödinger equation is investigated. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006
We introduce the de Broglie-Bohm causal interpreation of quantum mechanics and compare it to the standard interpretation of quantum mechanics, the Copenhagen interpretation. We examine the possibility of experimentally distinguishing between the two theories, as well as the potential for the causal interpretation to more easily bridge the gap between the physics of the quantum and classical worlds. We then use the causal interpretation to construct a deterministic model of the helium atom in which the two electrons move along trajectories through space and time about a stationary nucleus. The dynamics are governed by the non-relativistic Schrödinger equation and the spin vectors of both electrons are assumed to be constant along their respective trajectories. We examine the Bohmian trajectories associated with (approximations to) eigenstates of the helium Hamiltonian as well as the trajectories associated with some non-eigenstates. We also compute an approximation to the ground state energy of the helium atom using a representation of the helium wavefunction in terms of hydrogenic eigenfunctions which is motivated by a perturbation approach.
It is shown that Fermi-Dirac statistics is guaranteed by the Dirac current, from which spin-dependent quantum velocity fields and spin-dependent quantum trajectories can be inferred. Pauli's exclusion principle is demonstrated using the spin-dependent quantum trajectories. The Dirac current, unlike the Schroedinger current, is nonzero for stationary bound states due to the permanent magnetic moment of the electron. It is of order c{sup 0} in agreement with observation that Fermi-Dirac statistics is independent of electronic velocity. In summary the physical basis for exchange-correlation is found in Dirac's equation, although Schroedinger's equation may be used to evaluate the Dirac current in the nonrelativistic regime of electronic velocity.
In this paper we propose an ab initio method to solve quantum many-body problems of molecular dynamics where both electronic and nuclear degrees are represented by ensembles of trajectories and guiding waves in physical space. Both electrons and nuclei can be treated quantum mechanically where the guiding waves obey a set of coupled Schrodinger equations (quantum-quantum description) or, alternatively, coupled Schrodinger-Newtonian equations are solved for the quantum-classical approximation. The method takes into account local and nonlocal quantum correlation effects in a self-consistent manner. The general formalism is applied to one- and two-dimensional hydrogen molecules subjected to a strong ultrashort optical pulse. Comparison is made with the results from the "exact" Ehrenfest molecular dynamics for the molecular ionization and for the evolution of the internuclear distance as the molecule dissociates.