The multipolar Hamiltonian of quantum electrodynamics is extensively employed in chemical and optical physics to treat rigorously the interaction of electromagnetic fields with matter. It is also widely used to evaluate intermolecular interactions. The multipolar version of the Hamiltonian is commonly obtained by carrying out a unitary transformation of the Coulomb gauge Hamiltonian that goes by the name of Power-Zienau-Woolley (PZW). Not only does the formulation provide excellent agreement with experiment, and versatility in its predictive ability, but also superior physical insight. Recently, the foundations and validity of the PZW Hamiltonian have been questioned, raising a concern over issues of gauge transformation and invariance, and whether observable quantities obtained from unitarily equivalent Hamiltonians are identical. Here, an in-depth analysis of theoretical foundations clarifies the issues and enables misconceptions to be identified. Claims of non-physicality are refuted: the PZW transformation and ensuing Hamiltonian are shown to rest on solid physical principles and secure theoretical ground.

Quantum electrodynamics (QED) is the physical theory that describes the interaction of electrons and photons at a fundamental level. Its characteristic feature is that the radiation field, as well as the system of material particles, obeys the postulates of quantum mechanics. A rigorous non-relativistic formulation of this theory applicable to atoms and molecules has also been developed and applied with outstanding success to a number of processes of interest to chemical physicists, being most commonly explicated for a system of charged particles coupled to the electromagnetic field, with the latter second quantized. Calculations are subsequently carried out in the Schrödinger picture. In the last twenty-five years or so, considerable work on Coulomb gauge QED of molecules has been performed in the Heisenberg representation of quantum mechanics by adopting a completely field theoretic point of view. The methods and results of this approach, which offer significant advantages over conventional perturbative techniques for the solution of a number of problems, are reviewed. Beginning with the second quantized multipolar Hamiltonian, the Heisenberg equations of motion for the fermion and boson creation and annihilation operators are obtained. In the electric dipole approximation these are used to evaluate the Maxwell field operators in the proximity of a source in series of powers of the transition moment on iteration. Comparison is then made with the analogous fields computed in the minimal-coupling scheme. Formulae are also given for the fields of a moving source of charge. Two observables of the electromagnetic field associated with a stationary distribution of charge, namely the Poynting vector and the energy density, are then calculated. The source fields are then used in a response theory formalism to calculate the resonant transfer of energy between an excited and an unexcited pair of molecules, and the retarded van der Waals dispersion energy shift between two excited electric dipole polarizable molecules, from which the results when one or both of the pair is in the ground electronic state, are easily derivable. Extension of response theory to many-body dispersion forces is then outlined, with explicit results being given for the retarded correction to the Axilrod–Teller–Muto three-body interaction energy.

A general expression is derived for the matrix element for the resonant transfer of energy between an initially excited donor species and an acceptor moiety in the ground state, with each entity possessing an electric multipole moment of arbitrary order. In the quantum electrodynamical framework employed, the coupling between the pair is mediated by the exchange of a single virtual photon. The probability amplitude found from second-order perturbation theory is a product of the electric moments located at each center and the resonant multipole-multipole interaction tensor. Using the Fermi golden rule, a general formula for the rate of energy transfer is obtained. As an illustration of the efficacy of the theory developed, rates of excitation energy exchange are calculated for systems interacting through dipole-quadrupole, dipole-octupole, quadrupole-quadrupole, and the familiar dipole-dipole coupling. For each of the cases examined, the near- and far-zone limits of the migration rate are calculated from the result valid for all donor-acceptor separations beyond wave function overlap. Expression of the octupole contribution to the transfer rate in terms of its irreducible components of weights 1 and 3 leads to new features. The octupole weight-1 term is found to contribute only when the interaction is retarded, while the dipole-octupole weight-1 contribution appears as a higher-order correction term to the dipole-dipole rate. Order of magnitude estimates are given for the contributions of dipole-quadrupole and dipole-octupole terms relative to the leading dipole-dipole rate for near-, intermediate-, and far-zone separations to further understand the role played by higher multipole moments in the transfer of excitation and the mechanism dominating the process.

An overview is given of the molecular quantum electrodynamical (QED) theory of resonance energy transfer (RET). In this quantized radiation field description, RET arises from the exchange of a single virtual photon between excited donor and unexcited acceptor species. Diagrammatic time-dependent perturbation theory is employed to calculate the transfer matrix element, from which the migration rate is obtained via the Fermi golden rule. Rate formulae for oriented and isotropic systems hold for all pair separation distances, R, beyond wave function overlap. The two well-known mechanisms associated with migration of energy, namely the R⁻⁶ radiationless transfer rate due to Förster and the R⁻² radiative exchange, correspond to near- and far-zone asymptotes of the general result. Discriminatory pair transfer rates are also presented. The influence of an environment is accounted for by invoking the polariton, which mediates exchange and by introducing a complex refractive index to describe local field and screening effects. This macroscopic treatment is compared and contrasted with a microscopic analysis in which the role of a neutral, polarizable and passive third-particle in mediating transfer of energy is considered. Three possible coupling mechanisms arise, each requiring summation over 24 time-ordered diagrams at fourth-order of perturbation theory with the total rate being a sum of two- and various three-body terms.

One of the key frameworks for developing the theory of light–matter interactions in modern optics and photonics is quantum electrodynamics (QED). Contrasting with semiclassical theory, which depicts electromagnetic radiation as a classical wave, QED representations of quantized light fully embrace the concept of the photon. This tutorial review is a broad guide to cutting-edge applications of QED, providing an outline of its underlying foundation and an examination of its role in photon science. Alongside the full quantum methods, it is shown how significant distinctions can be drawn when compared to semiclassical approaches. Clear advantages in outcome arise in the predictive capacity and physical insights afforded by QED methods, which favors its adoption over other formulations of radiation–matter interaction.

The influence of a third molecule on the rate of resonance energy transfer is studied using diagrammatic perturbation theory within the framework of molecular quantum electrodynamics. Two distinct mechanisms are identified. One corresponds to direct transfer between donor and acceptor while the other involves relay of energy by the third species. Fermi Golden rule transition rates valid for all separation distances beyond wave function overlap are evaluated for these two processes as well as for the interference term between direct and indirect exchange, thereby extending previous work which was limited to the near-zone only. Short- and long-range limits are also obtained in each case. It is found that in the near-zone the indirect rate contribution exhibits inverse sixth power dependence on relative distances of emitter and absorber relative to the third body, in contrast to its far-zone counterpart, which exhibits inverse square behavior. The interference term, however, displays inverse cubic dependence on all three distance vectors at short-range and inverse behavior in the far-zone. Interestingly, for a collinear arrangement of the three molecules in the near-zone, the interference term is negative, reducing the overall rate of energy transfer. The results obtained are interpreted in terms of microscopic and macroscopic pictures of transfer occurring within a surrounding medium.