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.
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.
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.
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.
We consider a quantum particle as a wave packet in the coordinate space. When the conjugate wave packet in the momentum space is considered, we find that the group velocities of these two wave packets, which describe the particle dynamics, are in agreement with the Hamilton equations only if in the time dependent phases one considers the Lagrangian instead of the Hamiltonian which leads to the conventional Schrodinger equation. We define a relativistic quantum principle asserting that a quantum particle has a finite frequency spectrum, with a cutoff propagation velocity c as a universal constant not depending on the coordinate system, and that any time dependent phase variation is the same in any system of coordinates. From the time dependent phase invariance, the relativistic kinematics is obtained. We consider two types of possible interactions: 1) An interaction with an external field, by a modification of the time dependent phase differential with the terms proportional to the differentials of the space-time coordinates multiplied with the components of this field four-potential, and 2) an interaction by a deformation of the space-time coordinates, due to a gravitational field. From the invariance of the time dependent phase with field components, we obtain a mechanical force of the form of Lorentz’s force, and three Maxwell equations: The Gauss-Maxwell equations for the electric and magnetic fluxes, and the Faraday-Maxwell equation for the electromagnetic induction. When the fourth equation, Ampere-Maxwell, is considered, the interaction field takes the form of the electromagnetic field. For a low propagation velocity of the particle waves, we get a packet of waves with the time dependent phases proportional to the relativistic Hamiltonian, as in Dirac’s famous theory of spin, and a slowly-varying amplitude with a phase proportional to the momentum and this velocity. In the framework of our theory, the spin is obtained as an all quantum effect, without any additional assumption to the quantum theory. When a space-time deformation is considered in the time dependent phase of a quantum particle, from the group velocity we get the particle dynamics according to the general theory of relativity. In this way, the relativistic dynamics, the electromagnetic field, and the spin of a quantum particle are obtained only from the invariance of the time dependent phases of the particle wave functions.
Dirac's equation with static external fields is considered as an equation of relativistic quantum theory, which describes the quantum dynamics of an electron in four-dimensional space-time. It is shown that the Dirac electron has only one intrinsic degree of freedom -- spin. The quantum ensemble of an electron with a given energy consists of two inseparable from each other subensembles of heavy and light spin-1/2 quasiparticles to have opposite (relative) intrinsic parities. In the case of electrical scalar potential nonuniform in the direction of a particle motion, these subensembles behave as analogs of the electrical and magnetic components of the plane monochromatic electromagnetic wave propagating in a dispersive medium, nonuniform in the direction of a wave motion. The role of states with negative energies and the properties of the velocity operator are explained.
Abstract The Schrödinger–Pauli (SP) theory of electrons in an electromagnetic field explicitly accounts for the electron spin moment. The many‐electron theory is complemented via a new descriptive perspective namely, that of the individual electron via its equation of motion or “Quantal Newtonian” first law. The law is in terms of ‘classical’ fields whose sources are quantum mechanical expectation values of Hermitian operators taken with respect to the system wave function. The law states that each electron experiences an external and an internal field, the sum of which vanish. The external field is the sum of the binding electrostatic and a Lorentz field. The internal field is a sum of fields representative respectively of electron correlations due to the Pauli principle and Coulomb repulsion; the electron density; kinetic effects; and an internal magnetic field. The energy can be expressed in integral virial form in terms of these fields. The law is elucidated by application to the 23S state of a quantum dot in a magnetic field. It is proved that the Hamiltonian is an exactly known and universal functional of the wave function. This generalizes the SP equation, and reveals that its eigenfunctions and eigenvalues may be determined self‐consistently. A quantal density functional theory (QDFT) of the SP system is developed whereby additional properties are determined. A physical interpretation of Spin‐DFT based on the QDFT mapping is provided. Further generalizations of the present work to the temporal case, and relativistic Dirac theory, are proposed.