No abstract

Optical trapping is a well-established technique that is increasingly used on biological substances and nanostructures. Chirality, the property of objects that differ from their mirror image, is also of significance in such fields, and a subject of much current interest. This review offers insight into the intertwining of these topics with a focus on the latest theory. Optical trapping of nanoscale objects involves forward Rayleigh scattering of light involving transition dipole moments; usually these dipoles are assumed to be electric although, in chiral studies, magnetic dipoles must also be considered. It is shown that a system combining optical trapping and chirality could be used to separate enantiomers. Attention is also given to optical binding, which involves light induced interactions between trapped particles. Interesting effects also arise when binding is combined with chirality.

On the propagation of resonant radiation through an optically dense system, photon capture is commonly followed by one or more near-field transfers of the resulting optical excitation. The process invokes secondary changes to the local electronic environment, shifting the electromagnetic interactions between participant chromophores and producing modified intermolecular forces. From the theory it emerges that energy transfer, when it occurs between chromophores with electronically dissimilar properties, can itself generate significant changes in the intermolecular potentials. This report highlights specific effects that can be anticipated when laser light propagates across an interface between differentially absorbing components in a model energy transfer system.

The Coulombic coupling of electric dipole (E1) transition moments is the most commonly studied and widely operative mechanism for energy migration in multichromophore systems. However a significant number of exceptions exist, in which donor decay and/or acceptor excitation processes are E1-forbidden. The alternative transfer mechanisms that can apply in such cases include roles for higher multipole transitions, exciton- or phonon-assisted interactions, and non-Coulombic interactions based on electron exchange. A quantum electrodynamical formulation provides a rigorous basis to assess the first of these, specifically addressing the relative significance of higher multipole contributions to the process of energy transfer in donor-acceptor systems where electric dipole transitions are precluded by symmetry. Working within the near-zone limit, where donor-acceptor separations are small in comparison to the chromophore scale, the analysis highlights the contributions of both electric quadrupole-electric quadrupole (E2-E2) coupling and the seldom considered second-order electric dipole-electric dipole (E1(2)-E1(2)) coupling. For both forms of interaction, experimentally meaningful rate equations are secured by the use of orientational averaging, and the mechanisms are analyzed with reference to systems in which E1-forbidden transitions are commonly reported.