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International Journal of Quantum Chemistry

Electron trajectories in molecular orbitals

Isaiah Sumner, Hannah Anthony

Published Jul 16, 2020• 2 citations
Publisher

Abstract

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.

DOI
10.1002/qua.26371

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Transcending its origin in the debate on the interpretation of quantum theory, the continuous deterministic trajectory has proved a potent tool in computational quantum mechanics (an excellent introduction to numerical trajectory techniques is provided by Wyatt’s text [1]). It is straightforward to develop a method to derive the timedependent Schrödinger equation from a single-valued continuum of spacetime trajectories, and supply a corresponding exact formula for the wavefunction [2].Anatural language for this theory of evolution is offered by the hydrodynamic analogy, in which wave mechanics corresponds to the Eulerian picture (as shown by Madelung [3]) and the trajectory theory to the Lagrangian picture. The Lagrangian model for the quantum fluid may be developed from a variational principle involving a specific interaction potential (the quantum internal potential energy), and the Euler-Lagrange equations imply a nonlinear partial differential equation to calculate the trajectories of the fluid particles as functions of their initial coordinates and the initial wavefunction. The latter supplies two sets of data to the particle model: the initial density (via the amplitude) and the initial velocity (via the phase). The time-dependent wavefunction is then computed via the standard map between the Lagrangian coordinates and the Eulerian fields.
Bohmian mechanics, developed by Bohm in 1952, provides an alternative interpretation to nonrelativistic quantum mechanics [1-3]. In the hydrodynamic formulation of quantum mechanics, the continuity equation and the quantum Hamilton-Jacobi equation (QHJE) are obtained by substituting the wave function expressed in terms of the real amplitude and the real action function into the time-dependent Schrödinger equation. Bohm’s analytical approach has been used to compute and interpret realvalued quantum trajectories from a precomputed wave function for a diverse range of physical processes [3-8]. In the synthetic approach, the quantum trajectory method has been developed as a computational tool to generate the wave function by evolving ensembles of real-valued quantum trajectories through the integration of the hydrodynamic equations on the fly [9]. Remarkable progress has been made in the use of T&F Cat # K11224, Chapter 18, Page 284, 15-9-2010 real-valued quantum trajectories for solving a wide range of quantum mechanical problems [10].
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