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

Expanded horizons for generating and exploring optical angular momentum in vortex structures

Spin provides for a well-known extension to the information capacity of nanometer-scale electronic devices. Spin transfer can be effected with high fidelity between quantum dots, this type of emission being primarily associated with emission dipoles. However, in seeking to extend the more common spectroscopic connection of dipole transitions with orbital angular momentum, it has been shown impossible to securely transmit information on any other multipolar basis – partly because point detectors are confined to polarization measurement. Standard polarization methods in optics provide for only two independent degrees of freedom, such as the circular states of opposing handedness associated with photon spin. Complex light beams with structured wave-fronts or vector polarization do, however, offer a basis for additional degrees of freedom, enabling individual photons to convey far more information content. A familiar example is afforded by Laguerre-Gaussian modes, whose helically twisted wave-front and vortex fields are associated with orbital angular momentum. Each individual photon in such a beam has been shown to carry the entire spatial helical-mode information, supporting an experimental basis for sorting beams of different angular momentum content. One very recent development is a scheme for such optical vortices to be directly generated through electronic relaxation processes in structured molecular chromophore arrays. © (2013) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE)

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

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

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

Chiral discrimination in optical binding

The laser-induced intermolecular force that exists between two or more particles in the presence of an electromagnetic field is commonly termed “optical binding.” Distinct from the single-particle forces that are at play in optical trapping at the molecular level, the phenomenon of optical binding is a manifestation of the coupling between optically induced dipole moments in neutral particles. In other, more widely known areas of optics, there are many examples of chiral discrimination—signifying the different response a chiral material has to the handedness of an optical input. In the present analysis, extending previous work on chiral discrimination in optical binding, a mechanism is identified using a quantum electrodynamical approach. It is shown that the optical binding force between a pair of chiral molecules can be significantly discriminatory in nature, depending upon both the handedness of the interacting particles and the polarization of the incident light, and it is typically several orders of magnitude larger than previously reported

Optical vortex mode generation by nanoarrays with a tailored geometry

Light generated with orbital angular momentum, commonly known as an optical vortex, is widely achieved by modifying the phase structure of a conventional laser beam through the utilization of a suitable optical element. In recent research, a process has been introduced that can produce electromagnetic radiation with a helical wave-front directly from a source. The chirally driven optical emission originates from a hierarchy of tailored nanoscale chromophore arrays arranged with a specific propeller-like geometry and symmetry. In particular, a nanoarray composed of n particles requires each component to be held in a configuration with a rotation and associated phase shift of 2 π/n radians with respect to its neighbor. Following initial electronic excitation, each such array is capable of supporting delocalized doubly degenerate excitons, whose azimuthal phase progression is responsible for the helical wave-front. Under identified conditions, the relaxation of the electronically-excited nanoarray produces structured light in a spontaneous manner. Nanoarrays of escalating order, i.e. those containing an increasing number of components, enable access to a set of topological charges of higher order. Practical considerations for the development of this technique are discussed, and potential new applications are identified. © (2014) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE)

Child Well-being in the Pacific Rim

This study extends previous efforts to compare the well-being of children using multi-dimensional indicators derived from sample survey and administrative series to thirteen countries in the Pacific Rim. The framework for the analysis of child well-being is to organise 46 indicators into 21 components and organise the components into 6 domains: material situation, health, education, subjective well-being, living environment, as well as risk and safety. Overall, Japan, Singapore and Taiwan have the highest child well-being and Thailand, Indonesia and the Philippines the lowest. However, there are substantial variations between the domains. Japan and Korea perform best on the material well-being of children and also do well on health and education but they have the lowest subjective well-being among their children by some margin. There is a relationship between child well-being and GDP per capita but children in China have higher well-being than you would expect given their GDP and children in Australia have lower well-being. The analysis is constrained by missing data particularly that the Health Behaviour of School-Aged Children Survey is not undertaken in any of these countries

Raman scattering mediated by neighboring molecules

Raman scattering is most commonly associated with a change in vibrational state within individual molecules, the corresponding frequency shift in the scattered light affording a key way of identifying material structures. In theories where both matter and light are treated quantum mechanically, the fundamental scattering process is represented as the concurrent annihilation of a photon from one radiation mode and creation of another in a different mode. Developing this quantum electrodynamical formulation, the focus of the present work is on the spectroscopic consequences of electrodynamic coupling between neighboring molecules or other kinds of optical center. To encompass these nanoscale interactions, through which the molecular states evolve under the dual influence of the input light and local fields, this work identifies and determines two major mechanisms for each of which different selection rules apply. The constituent optical centers are considered to be chemically different and held in a fixed orientation with respect to each other, either as two components of a larger molecule or a molecular assembly that can undergo free rotation in a fluid medium or as parts of a larger, solid material. The two centers are considered to be separated beyond wavefunction overlap but close enough together to fall within an optical near-field limit, which leads to high inverse power dependences on their local separation. In this investigation, individual centers undergo a Stokes transition, whilst each neighbor of a different species remains in its original electronic and vibrational state. Analogous principles are applicable for the anti-Stokes case. The analysis concludes by considering the experimental consequences of applying this spectroscopic interpretation to fluid media; explicitly, the selection rules and the impact of pressure on the radiant intensity of this process

Resonance energy transfer: The unified theory revisited

Resonanceenergy transfer (RET) is the principal mechanism for the intermolecular or intramolecular redistribution of electronic energy following molecular excitation. In terms of fundamental quantum interactions, the process is properly described in terms of a virtual photon transit between the pre-excited donor and a lower energy (usually ground-state) acceptor. The detailed quantum amplitude for RET is calculated by molecular quantum electrodynamical techniques with the observable, the transfer rate, derived via application of the Fermi golden rule. In the treatment reported here, recently devised state-sequence techniques and a novel calculational protocol is applied to RET and shown to circumvent problems associated with the usual method. The second-rank tensor describing virtual photon behavior evolves from a Green’s function solution to the Helmholtz equation, and special functions are employed to realize the coupling tensor. The method is used to derive a new result for energy transfer systems sensitive to both magnetic- and electric-dipole transitions. The ensuing result is compared to that of pure electric-dipole–electric-dipole coupling and is analyzed with regard to acceptable transfer separations. Systems are proposed where the electric-dipole–magnetic-dipole term is the leading contribution to the overall rate