Abstract 1. In a recent paper Dirac* has brilliantly removed the defects before existing in the mechanics of the electron, and has shown how the phenomena usually called the “ spinning electron ” fit into place in the complete theory. He applies to he problem the method of q-numbers and, using non-commutative algebra, exhibits the properties of a free electron, and of an electron in a central field of electric force. In a second paper † he also discusses the rules of combination and the Zeeman effect. There are probably readers who will share the present writer’s feeling that the methods of non-commutative algebra are harder to follow, and certainly much more difficult to invent, than are operations of types long familiar to analysis. Wherever it is possible to do so, it is surely better to present the theory in a mathematical form that dates from the time of Laplace and Legendre, if only because the details of the calculus have been so much more thoroughly explored. So the object of the present work is to take Dirac’s system and treat it by the ordinary methods of wave calculus. The chief point of interest is perhaps the solution of the problem of the central field, which can be carried out exactly and leads to Sommerfeld’s original formula for the hydrogen levels. But it is also of some interest to exhibit the relationship of the new theory to the previous equations which were derived empirically by the present writer.* It appears that those equations were an approximation to the new ones, derived by an approximate elimination of two of Dirac’s four wave functions. We shall also review a few other points connected with the free electron, the emission of radiation from an atom and its magnetic moment, and shall outline a discussion of the Zeeman effect.
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.
We begin our study of atomic physics by relying on the phenomenological notions summarized in chapter 1 and by fully exploiting the quantum mechanical formalism outlined in chapter 2. A hierarchy of approximations will be introduced in the first instance to describe the hydrogen atom, which allows one to focus on the main features of its energy spectrum and quantum properties, including the key ‘atomic orbital’ concept. Next, these results will be extended to the more general case of hydrogenic atoms. The physical picture will be made more rigorous by introducing the magnetic interactions, included those linked to the intrinsic spin degree of freedom, leading to the full description of the fine and hyperfine structure of one-electron atoms. The effects of a static external magnetic or electric field will be eventually discussed by calculating the corresponding energy shifts and splittings of the energy levels.
The problem of Rydberg atomic spectra in crossed electric F and magnetic B fields (combined Stark–Zeeman effects), as well as an oscillating electric field are under consideration. The main problem is the great array of radiative transitions between the Rydberg atomic states. The different versions of semiclassical approaches are applied for the solution of the problem. New approximate selection rules are established to simplify the matrix elements of radiative transitions, making it possible to reduce the complex expressions of Gordon’s hypergeometric series to the trivial trigonometric functions. Simple analytical formulas for the dipole matrix elements of a Rydberg hydrogen-like atom in external crossed electric and magnetic fields for Hnα are obtained. The specific calculations are presented for n = 10 to 9 transition both for parallel and perpendicular orientations of F–B fields. The result of Blokhintsev for a single Stark component in oscillating field is generalized for the array of radiative transitions between Rydberg atomic states. Such spectra with large values of modulation index are compared with static ones.
A simple and accurate variational method is formulated and applied to the ground and excited states of the hydrogen atom as well as the hydrogen molecule ion in a homogeneous magnetic field of arbitrary strength. For the ground state, the electronic wave function o is assumed to be a function of a single, appropriately chosen variable R which contains a variational parameter. The functional form of o, and the corresponding energy, are determined by solving a Schr6dinger- like equation, in which the variational parameter appears explicitly in the kinetic and potential energy terms. The variational parameter is optimized by minimizing the lowest eigenvalue of the equation. Excited states may also be obtained by a slight modification of the method, and explicit calculations are carried out for the m1 = - 1 first excited state of hydrogen and the ( )-state of H2 +. Numerical comparisons are made with some recent papers in the literature. Subject headings: atomic processes - magnetic fields - molecular processes - quantum mechanics
We investigate the helium dimer in strong magnetic fields, focusing on the spectrum of low-lying electronic states and their dissociation curves, at the full configuration-interaction level of theory. To address the loss of cylindrical symmetry and angular momentum as a good quantum number for nontrivial angles between the bond axis and magnetic field, we introduce the almost quantized angular momentum (AQAM) and show that it provides useful information about states in arbitrary orientations. In general, strong magnetic fields dramatically rearrange the spectrum, with the orbital Zeeman effect bringing down states of higher angular momentum below the states with pure σ character as the field strength increases. In addition, the spin Zeeman effect pushes triplet states below the lowest singlet; in particular, a field of one atomic unit is strong enough to push a quintet state below the triplets. In general, the angle between the bond axis and the magnetic field also continuously modulates the degree of σ, π, and δ character of bonds and the previously identified perpendicular paramagnetic bonding mechanism is found to be common among excited states. Electronic states with preferred skew field orientations are identified and rationalized in terms of permanent and induced electronic currents.