The calculation of the retarded fourth-order resonance interaction between identical molecules with one shared quantum of excitation energy is described. The interaction is calculated in the electric dipole approximation for molecular transitions with the help of time-ordered graphs and a reduced Hamiltonian which treats molecule-photon and molecule-molecule interactions on the same footing. Interactions involving spins, valence forces and permanent electric or magnetic multipoles are not considered. In the near and wave zones the leading terms of the retarded interaction are proportional to R -6 and R -2 respectively, where R is the intermolecular separation.
Abstract Radiation damping of three atoms in a radiation field is studied for both a linear and closed‐chain configuration. One atom of the system is initially excited. Use is made of the Heitler‐Ma perturbation procedure up to second order. The discussion is developed in terms of the symmetry of the interactions within the system. The interactions arising from dipole transitions perpendicular to the plane of the closed chain are shown to be similar to the interactions in a two‐atom system, and the results are extended to cover larger rings.
The effect of correlations between an absorber atom and perturbers in the binary-collision approximation are applied to degenerate atomic systems. A generalized absorption profile which specifies the final state of the atom after an absorption event is related to the total intensities of Rayleigh scattering and fluorescence from the atom. It is suggested that additional dynamical information to that obtainable from ordinary absorption experiments is required in order to describe redistributed atomic radiation. The scattering of monochromatic radiation by a degenerate atom is computed in a binary-collision approximation; an equation of motion is derived for the correlation function which is valid outside the quantum-regression regime. Solutions are given for the weak-field conditions in terms of generalized absorption and emission profiles that depend on the indices of the atomic multipoles.
Atoms and ions containing residual bound electrons do not quite resemble the simple harmonic oscillator model used so successfully in the classical theory of radiation. However, replacing the atoms or ions with sets of harmonic oscillators of a great number of discrete resonance frequencies and having various amplitudes, together with the results of classical radiation theory, go a long way toward a quantitative description of emission or absorption spectra. The set of resonance frequencies is obtained from measured or calculated energy levels using Ritz's combination principle. The amplitudes are associated with matrix elements of appropriate quantum mechanical operators between wave functions of the two energy eigenstates involved at a given frequency. In other words, quantities of the emitters, absorbers, or scatterers are described quantum-mechanically, whereas the electromagnetic field is treated classically. Such semi-classical description of matter-electromagnetic field interactions became unnecessary very early in the development of quantum theory. It will therefore not be discussed in any detail. Instead, we will begin immediately with the combined theory of matter and radiation (Heitler 1954, Dirac 1958, Loudon 1983). Quantum theory of particles and fields There are various ways to also quantize the electromagnetic fields (Cohen-Tannoudji, DuPont-Roc and Grynberg 1989), of which that performed on the combined Hamiltonian equations of motion for the field-matter system is followed here.
The interaction of an atomic system with an unquantized electromagnetic field is studied by means of the Heisenberg-operator equations of motion. The electromagnetic fields created by the atom are taken into account by assuming that the charge and probability current densities are the actual charge and current source terms in Maxwell's equation. When Ehrenfest's theorem is written to order (1/c
)2, the equations of motion are found to have a constant of motion that can be interpreted as stating that the sum of the atomic energy, energy of interaction, and energy stored in the electromagnetic field is constant. This constant of integration can be expressed as an expectation of a new semiclassical Hamiltonian that now includes the effects of the atomic self-fields to order 1/
c2. This Hamiltonian is related to the classical Darwin Lagrangian. Since the new approximate Hamiltonian is the sum of an atomic and a field Hamiltonian, it provides a formulation of semiclassical radiation theory that is formally close to the usual formulation of quantum electrodynamics. A Schr\"odinger equation can be derived by applying the variational principle to the expectation of the new Hamiltonian. The result is a nonlinear integro-differential equation, in \ensuremath{\Psi}, which is somewhat similar to Hartree's self-consistent equation for a multielectron atom.When the Heisenberg equations are written to include the next-higher-order terms, 1/
c3, it is found that the total energy of the atom and the electromagnetic field in the vicinity of the atom decreases at a rate that is given by the Larmor power formula (2
e2/3
c3)(d〈v〉/dt
)2, where 〈v〉 is the quantum-mechanical expectation of the electron's velocity operator. This approximate formulation of semiclassical radiation theory is applied to semiclassical calculations of atomic radiative shifts. It is then shown that, if some retardation effects are included to all orders of 1/c in the vector potential, the semiclassical analysis provides a formula for radiative energy-level shifts that are time dependent and that contain coefficients similar to the starting point of the Bethe calculation of the Lamb shift. The incorporation of mass renormalization in semiclassical theory is then discussed.
The frequency distribution of resonant radiation emitted by a system of two identical interacting atoms is calculated. The separation between the atoms is assumed to be much larger than the size of their charge distributions. Initially one atom is excited while the second one is in the ground state. The two atoms are coupled through the radiation field and the electrostatic interaction. For not too large internuclear separations the line shape of the emitted radiation exhibits two distinct peaks, and the general features are identical with the result obtained from resonance fluorescence scattering. In the decay process, however, there is equal probability of scattering through the symmetric and antisymmetric states, and thus the peak heights of the emitted radiation are different from the ones in the resonance fluorescent case. For large internuclear separations the two peaks merge into the one characteristic of the line shape of a single isolated atom.