A thorough unified treatment is given of the quantum-mechanical operators and wave functions for a molecular system (composed of
N moving charged particles) in static uniform electric and magnetic fields
E and
B. The treatment is rigorous within the nonrelativistic approximation. The system may either be neutral or charged. The fields may have arbitrary intensities and orientations. Close correspondence is maintained between the classical and quantum-mechanical treatments. The wave functions are expressed both in the time-independent energy representation and in time-dependent wave packets. Three types of momentum play important roles. For single-particle systems they are the canonical momentum
P, the mechanical momentum $\mathit{\ensuremath{\Pi}}=\mathit{P}\ensuremath{-}(\frac{e}{c})\mathit{A}=M\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$, and the pseudomomentum $\mathcal{K}=\mathit{\ensuremath{\Pi}}\ensuremath{-}(\frac{e}{c})\mathit{R}\ifmmode\times\else\texttimes\fi{}\mathit{B}\ensuremath{-}e\mathit{E}t$. The pseudomomentum is a constant of the motion. Except in the absence of magnetic fields, not all of the components of either $\mathit{\ensuremath{\Pi}}$ or
K commute. This complicates the quantum-mechanical formalism. The components of the pseudomomentum have simple classical interpretations, and in quantum mechanics they are related to the operator which performs a boost to a reference frame moving with constant velocity
v. In this moving frame, the electric field intensity is ${\mathit{E}}^{\ensuremath{'}}=\mathit{E}+(\frac{\mathit{v}}{c})\ifmmode\times\else\texttimes\fi{}\mathit{B}$. Thus, in a frame moving with the drift velocity ${\mathit{v}}_{d}=(\frac{c}{{B}^{2}})\mathit{E}\ifmmode\times\else\texttimes\fi{}\mathit{B}$, the components of the electric field intensity perpendicular to
B vanish. In this paper, the velocity boost operators are used to show the relationships between wave functions expressed in reference frames moving with repsect to each other. The dynamics of the
N-particle systems are simplified by making the Power-Zienau-Woolley transformation (which reduces as a special case to a unitary transformation used by Lamb) and by using center-of-mass and internal coordinates. Generalizing previous works, it is shown how the pseudomomentum is involved in separating these degrees of freedom for
N particles in both
E and
B. For neutral molecules, the Schr\"odinger equation is "pseudoseparated" and the internal degrees of freedom are coupled to the center of mass motion only by the "motional Stark Effect," which involves the constant of motion
K. For ionic systems, only one component of the center of mass is coupled to the internal motion. Quantitative estimates of the weak center-of-mass coupling are made for both neutral and ionic
n=1 and
n=2 quantum states of two-body systems by perturbation expansions in powers of the field strengths. In the usual nonrigorous treatments of systems in magnetic fields, no distinction is made between $\mathit{\ensuremath{\Pi}}$ and
K and both are approximated by $M\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$, where
M is the mass of the molecule and
R is taken to be the classical orbital position of a single particle having the same mass and charge. This is an excellent approximation for ground-state molecules and ions in weak fields. However, the resulting errors can be much larger if the system is in either intense fields or high-lying states (e.g., Rydberg levels). These are the conditions under which the rigorous formalism should be most useful. The determination of the wave functions and energy levels for many-particle ionic systems is complicated due to the coupling with the center of mass. The suggestion is made that it might be useful to boost the reference frame so that it moves with the velocity $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{R}$ of a single classical particle. The Schr\"odinger equation in this frame could serve as a more suitable basis for perturbative or variational treatments.
For neutral molecules in a homogeneous magnetic field there exists a constant of motion, the pseudomomentum, which allows a complete pseudoseparation of the center-of-mass motion. For molecular ions a complete set of constants of motion is not known, neither exactly nor approximately. In this paper we investigate the structure an approximate constant of motion for a molecular ion can have in general and arrive at an interesting formula. An explicit approximate constant of motion that obeys this structure formula is derived from a physically intuitive picture that says that an approximately conserved quantity can be obtained as the pseudomomentum relative to the instantaneously fixed-nuclei center of charge of the system. Some special examples are discussed in detail.
A general method to treat the quantal two-body problem relativistically is developed on the line of Dirac's many-time theory. The case where two charged fermions interact with each other through the electromagnetic field is investigated as an example. We construct a canonical transformation which eliminates the electromagnetic field variables in the original Schrödinger equations, and derive the potential energy between two charged particles. Finally, some properties of the simultaneous wave equations for the system of two particles are discussed, and a method to treat the stationary state of that system is indicated.
Essentially, we solve the particle-field equations obtained in the matter distribution quantum mechanics. In the framework of this theory, a particle is described by a density amplitude function, we call wave function, as a packet of waves with the time dependent phases proportional to the relativistic Lagrangian. The mass quantization of such a particle, as a distribution of matter, is obtained from the equality of the spatial integral of the density with the mass as a characteristic of the relativistic dynamics of this matter. The particle dynamics, as a motion of a mass spatial distribution, is obtained from the equality of the wave propagation velocities with the distribution coordinate velocities. This description is a physical one, compared to the Schrödinger-Heisenberg description leading to unphysical results as a null velocity for the kinetic energy as a constant of motion, or Zitterbewegung. The description of a particle interaction with an electromagnetic field by additional Lagrangian terms, with a vector potential conjugated to coordinates, as in the Aharonov-Bohm effect, and an electric potential conjugated to time, leads to the Lorentz force, and the Maxwell equations. In the two conjugated spaces, of the coordinates and of the momentum, the dynamics of a quantum particle is described by propagation operators, depending on the coordinate-momentum product, applied to time dependent wave functions satisfying matter-field equations. Unlike the standard Schrödinger or Schrödinger-Dirac equations, depending only on the Hamiltonian operator, instead of the Hamiltonian these equations contain the Lagrangian, which, besides the Hamiltonian, include additional terms with an explicit dependence on velocity, as it is expected in a relativistic theory. We obtain the wave function of a particle-antiparticle system interacting with an electromagnetic field, as a wave packet of spinors propagating in space with finite dimensions, given by the finite definition domain of the density function, in the space of the matter-field momentum, as a constant of motion. We show that an electrically charged quantum particle, rotating in a central electric field, generates a vector potential with a magnetic field perpendicular to the rotational plane and an electric field in this plane. By a quantum transition, a photon is emitted in the particle rotational plane, with the magnetic field perpendicular to this plane, and the electric field contained in this plane. In this framework, the vector potential rotation is correlated to a particle momentum rotation, for the canonical matter-field momentum as a constant of motion, without any electromagnetic field radiated outside.
The approximate constant of motion introduced previously for the description of a charged system in a homogeneous magnetic field is interpreted physically as the kinetic momentum of the collective motion. The algebra satisfied by this operator and by the exact constants of motion describes the behavior in a magnetic field of a single particle possessing the total charge of the system. With this algebra, we generalize the approximate constant of motion and obtain a family of operators depending on arbitrary parameters. Canonical transformations based on these new operators separate the Hamiltonian into collective, internal, and coupling terms. These terms take the same form for charged and neutral systems although the collective energy represents different physical behaviors. The coupling between the internal and collective motions is small for some choices of the parameters if at least one particle is much heavier than the other ones.
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.