Nonlinear energy pooling in nanophotonic materials

Recently there has been considerable interest in the construction of photoactive organic materials designed to exhibit novel forms of optical nonlinearity. By exploiting the unique properties of these nanomaterials at high levels of photon flux, new possibilities emerge for applications in energy harvesting, low-threshold lasing, quantum logic devices, photodynamic therapy, etc. In particular, a detailed appraisal of the theory spotlights novel mechanisms for directed energy transfer and energy pooling in nanophotonic dendrimers. Characterized by a nonlinear dependence on the optical irradiance, these mechanisms fall into two classes: (a) those where two-photon absorption by individual donors is followed by transfer of the sum energy to the acceptor; (b) where the excitation of two electronically distinct but neighbouring donor groups is followed by a collective migration of their energy to a suitable acceptor. In each case these transfer processes are subject to minor dissipative losses, associated with intramolecular vibrational relaxation in the donor species. In this paper we describe in detail the balance of factors and the constraints that determines the favored mechanism, which include the excitation statistics, structure of the energy levels, selection rules, molecular architecture, the distribution of donors and acceptors, spectral overlap and coherence factors. Knowledge of these factors and the means for their optimization offers fresh insights into nanophotonic characteristics, and informs strategies for the design of new photoactive materials

Near-field manipulation of interparticle forces through resonant absorption, optical binding, and dispersion forces

The relative motions of two or more neutral particles, subject to optical trapping forces within a beam, are influenced by intrinsic inter-particle forces. The fundamental character of such forces is well-known and usually derives from dispersion interactions. However, the throughput of moderately intense (off-resonant) laser light can significantly modify the form and magnitude of these intrinsic forces. This optical binding effect is distinct from the optomechanical interactions involved in optical tweezers, and corresponds to a stimulated (pairwise) forward-scattering mechanism. In recent years, attention has begun to focus on optical binding effects at sub-micron and molecular dimensions. At this nanoscale, further manipulation of the interparticle forces is conceivable on the promotion of optically bound molecules to an electronic excited state. It is determined that such excitation may influence the intrinsic dispersion interaction without continued throughput of the laser beam, i.e. independent of any optical binding. Nevertheless, the forwardscattering mechanism is also affected by the initial excitation, so that both the optical binding and dispersion forces can be manipulated on input of the electromagnetic radiation. In addition, the rate of initial excitation of either molecule (or any energy transfer between them) may be influenced by an off-resonant input beam which, thus, acts as an additional actor in the modification of the interparticle force. A possible experimental set-up is proposed to enable the measurement of such changes in the interparticle coupling. © (2013) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE)

All-optical switching based on controlled energy transfer between nanoparticles in film arrays

The potentiality to exert optical control, over the migration of electronic excitation energy between particles with suitably disposed electronic levels, affords a basis for all-optical switching. Implemented in a configuration with nanoparticles arrayed in thin films, the process can offer an ultrafast parallel-processing capability. The mechanism is a nearfield transfer of energy from donor nanoparticles in one layer (written into an electronically excited state by the absorption of light) to counterpart acceptors; the transfer effect proves amenable to activation by non-resonant laser radiation. The possibility of optical control arises under conditions where the donor-acceptor energy transfer is rigorously forbidden in the absence of laser light, either on the grounds of symmetry or energetics. Under such conditions, optical switching can be produced by the throughput of a single off-resonant beam or, with more control options, by two coincident beams. In model electrodynamical calculations the transfer fidelity, signifying the accuracy of mapping an input to its designated output, can be identified and cast in terms of key optical and geometric characteristics. The results show that, at reasonable levels of laser intensity, cross-talk drops to insignificant levels. Potential applications extend beyond simple switching into all-optical elements for logic gates and optical buffers. © 2009 Society of Photo-Optical Instrumentation Engineers

On the detection of characteristic optical emission from electronically coupled nanoemitters

Optical emission from an electronically coupled pair of nanoemitters is investigated, in a new theoretical development prompted by experimental work on oriented semiconductor polymer nanostructures. Three physically distinct mechanisms for photon emission by such a pair, positioned in the near-field, are identified: emission from a pairdelocalized exciton state, emission that engages electrodynamic coupling through quantum interference, and correlated photon emission from the two components of the pair. Each possibility is investigated, in detail, by examination of the emission signal via explicit coupling of the nanoemitter pair with a photodetector, enabling calculations to give predictive results in a form directly tailored for experiment. The analysis incorporates both near- and far-field properties (determined from the detector-pair displacement), so that the framework is applicable not only to a conventional remote detector, but also a near-field microscope setup. The results prove strongly dependent on geometry and selection rules. This work paves the way for a broader investigation of pairwise coupling effects in the optical emission from structured nanoemitter arrays

Optically controlled resonance energy transfer:Mechanism and configuration for all-optical switching

In a molecular system of energy donors and acceptors, resonance energy transfer is the primary mechanism by means of which electronic energy is redistributed between molecules, following the excitation of a donor. Given a suitable geometric configuration it is possible to completely inhibit this energy transfer in such a way that it can only be activated by application of an off-resonant laser beam: this is the principle of optically controlled resonance energy transfer, the basis for an all-optical switch. This paper begins with an investigation of optically controlled energy transfer between a single donor and acceptor molecule, identifying the symmetry and structural constraints and analyzing in detail the dependence on molecular energy level positioning. Spatially correlated donor and acceptor arrays with linear, square, and hexagonally structured arrangements are then assessed as potential configurations for all-optical switching. Built on quantum electrodynamical principles the concept of transfer fidelity, a parameter quantifying the efficiency of energy transportation, is introduced and defined. Results are explored by employing numerical simulations and graphical analysis. Finally, a discussion focuses on the advantages of such energy transfer based processes over all-optical switching of other proposed forms. © 2008 American Institute of Physics

Molecular dynamics study of nanoparticle stability at liquid interfaces : effect of nanoparticle-solvent interaction and capillary waves

While the interaction of colloidal particles (sizes in excess of 100 nm) with liquid interfaces may be understood in terms of continuum models, which are grounded in macroscopic properties such as surface and line tensions, the behaviour of nanoparticles at liquid interfaces may be more complex. Recent simulations [D. L. Cheung and S. A. F. Bon, Phys. Rev. Lett. 102, 066103 (2009)] of nanoparticles at an idealised liquid-liquid interface showed that the nanoparticle-interface interaction range was larger than expected due, in part, to the action of thermal capillary waves. In this paper, molecular dynamics simulations of a Lennard-Jones nanoparticle in a binary Lennard-Jones mixture are used to confirm that these previous results hold for more realistic models. Furthermore by including attractive interactions between the nanoparticle and the solvent, it is found that the detachment energy decreases as the nanoparticle-solvent attraction increases. Comparison between the simulation results and recent theoretical predictions [H. Lehle and M. Oettel, J. Phys. Condens. Matter 20, 404224 (2008)] shows that for small particles the incorporation of capillary waves into the predicted effective nanoparticle-interface interaction improves agreement between simulation and theory

All-optical control of molecular fluorescence

We present a quantum electrodynamical procedure to demonstrate the all-optical control of molecular fluorescence. The effect is achieved on passage of an off-resonant laser beam through an optically activated system; the presence of a surface is not required. Following the derivation and analysis of the all-optical control mechanism, calculations are given to quantify the significant modification of spontaneous fluorescent emission with input laser irradiance. Specific results are given for molecules whose electronic spectra are dominated by transitions between three electronic levels, and suitable laser experimental methods are proposed. It is also shown that the phenomenon is sensitive to the handedness of circularly polarized throughput, producing a conferred form of optical activity