A retarded coupling approach to intermolecular interactions

A wide range of physical phenomena such as optical binding and resonance energy transfer involve electronic coupling between adjacent molecules. A quantum electrodynamical description of these intermolecular interactions reveals the presence of retardation effects. The clarity of the procedure associated with the construction of the quantum amplitudes and the precision of the ensuing results for observable energies and rates are widely acknowledged. However, the length and complexity of the derivations involved in such quantum electrodynamical descriptions increase rapidly with the order of the process under study. Whether through the use of time-ordering approaches, or the more expedient state-sequence method, time-consuming calculations cannot usually be bypassed. A simple and succinct method is now presented, which provides for a direct and still entirely rigorous determination of the quantum electrodynamical amplitudes for processes of arbitrarily high order. Using the approach, new results for optical binding in two- and three-particle systems are secured and discussed

Optical binding in nanoparticle assembly: Potential energy landscapes

Optical binding is an optomechanical effect exhibited by systems of micro- and nanoparticles, suitably irradiated with off-resonance laser light. Physically distinct from standing-wave and other forms of holographic optical traps, the phenomenon arises as a result of an interparticle coupling with individual radiation modes, leading to optically induced modifications to Casmir-Polder interactions. To better understand how this mechanism leads to the observed assemblies and formation of patterns in nanoparticles, we develop a theory in terms of optically induced energy landscapes exhibiting the three-dimensional form of the potential energy field. It is shown in detail that the positioning and magnitude of local energy maxima and minima depend on the configuration of each particle pair, with regards to the polarization and wave vector of the laser light. The analysis reveals how the positioning of local minima determines the energetically most favorable locations for the addition of a third particle to each equilibrium pair. It is also demonstrated how the result of such an addition subtly modifies the energy landscape that will, in turn, determine the optimum location for further particle additions. As such, this development represents a rigorous and general formulation of the theory, paving the way toward full comprehension of nanoparticle assembly based on optical binding

Laser-controlled fluorescence in two-level systems

The ability to modify the character of fluorescent emission by a laser-controlled, optically nonlinear process has recently been shown theoretically feasible, and several possible applications have already been identified. In operation, a pulse of off-resonant probe laser beam, of sufficient intensity, is applied to a system exhibiting fluorescence, during the interval of excited- state decay following the initial excitation. The result is a rate of decay that can be controllably modified, the associated changes in fluorescence behavior affording new, chemically specific information. In this paper, a two-level emission model is employed in the further analysis of this all-optical process; the results should prove especially relevant to the analysis and imaging of physical systems employing fluorescent markers, these ranging from quantum dots to green fluorescence protein. Expressions are presented for the laser-controlled fluorescence anisotropy exhibited by samples in which the fluorophores are randomly oriented. It is also shown that, in systems with suitably configured electronic levels and symmetry properties, fluorescence emission can be produced from energy levels that would normally decay nonradiatively. © 2010 American Chemical Society

Identifying the development in phase and amplitude of dipole and multipole radiation

The spatial variation in phase and the propagating wave-front of plane wave electromagnetic radiation are widely familiar text-book territory. In contrast, the developing amplitude and phase of radiation emitted by a dipole or multipole source generally receive less attention, despite the prevalence of these systems. There is additional complexity in such cases where, in consequence of retardation, the character and features significantly and progressively change as radiation propagates onwards, from the near-field and out towards the wave-zone. Readily developed analytical representations of the electric field, cast as a function of distance from the source, provide illuminating insights into the most prominent and distinctive properties of radiant electromagnetic emission. Graphical implementations and animations of the results prove particularly instructive in revealing the spatial form and temporal evolution of the emergent electromagnetic fields

Interparticle interactions:Energy potentials, energy transfer, and nanoscale mechanical motion in response to optical radiation

In the interactions between particles of material with slightly different electronic levels, unusually large shifts in the pair potential can result from photoexcitation, and on subsequent electronic excitation transfer. To elicit these phenomena, it is necessary to understand the fundamental differences between a variety of optical properties deriving from dispersion interactions, and processes such as resonance energy transfer that occur under laser irradiance. This helps dispel some confusion in the recent literature. By developing and interpreting the theory at a deeper level, one can anticipate that in suitable systems, light absorption and energy transfer will be accompanied by significant displacements in interparticle separation, leading to nanoscale mechanical motion