In the optical excitation of many nanoscale systems, the primary result of photon absorption is an electronic excitation that is typically followed by ultrafast relaxation processes. The losses associated with such relaxation generally produce a partial degradation of the optical energy acquired, before any ensuing photon emission occurs. Recent work has shown that the intensity and directional character of such emission may be significantly influenced through engagement with a completely off-resonant probe laser beam of sufficient intensity: the mechanism for this optical coupling is a secondorder nonlinearity. It is anticipated that the facility to actively control fluorescent emission in this way may lead to new opportunities in a variety of applications where molecular chromophores or quantum dots are used. In the latter connection it should prove possible to exploit the particle size dependence of the nonlinear optical dispersion, as well as that of the emission wavelength. Specific characteristics of the effect are calculated, and suitable experimental implementations of the mechanism are proposed. We anticipate that this all-optical control device may introduce significant new perspectives to fluorescence imaging techniques and other analytical applications.
In the optical excitation of many nanoscale systems, the primary result of photon absorption is an electronic excitation that is typically followed by ultrafast relaxation processes. The losses associated with such relaxation generally produce a partial degradation of the optical energy acquired, before any ensuing photon emission occurs. Recent work has shown that the intensity and directional character of such emission may be significantly influenced through engagement with a completely off-resonant probe laser beam of sufficient intensity: the mechanism for this optical coupling is a secondorder nonlinearity. It is anticipated that the facility to actively control fluorescent emission in this way may lead to new opportunities in a variety of applications where molecular chromophores or quantum dots are used. In the latter connection it should prove possible to exploit the particle size dependence of the nonlinear optical dispersion, as well as that of the emission wavelength. Specific characteristics of the effect are calculated, and suitable experimental implementations of the mechanism are proposed. We anticipate that this all-optical control device may introduce significant new perspectives to fluorescence imaging techniques and other analytical applications.
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.
A wide range of mechanisms is available for achieving rapid optical responsivity in material components. Amongst them, some of the most promising for potential device applications are those associated with an ultrafast response and a short cycle time. These twin criteria for photoresponsive action substantially favor optical, over most other, forms of response such as those fundamentally associated with photothermal, photochemical or optomechanical processes. The engagement of nonlinear mechanisms to actively control the characteristics of optical materials is not new. Indeed, it has been known for over fifty years that polarization effects of this nature occur in the optical Kerr effect – although in fluid media the involvement of a molecular reorientation mechanism leads to a significant response time. It has more recently emerged that there are other, less familiar forms of optical nonlinearity that can provide a means for one beam of light to instantly influence another. In particular, major material properties such as absorptivity or emissivity can be subjected to instant and highly localized control by the transmission of light with an off-resonant wavelength. This presentation introduces and compares the key electrodynamic mechanisms, discussing the features that suggest the most attractive possibilities for exploitation. The most significant of such mechanistic features include the off-resonant activation of optical emission, the control of excited-state lifetimes, the access of dark states, the inhibition or re-direction of exciton migration, and a coupling of stimulated emission with coherent scattering. It is shown that these offer a variety of new possibilities for ultrafast optical switching and transistor action, ultimately providing all-optical control with nanoscale precision.
Multiphoton fluorescence microscopy is now a well-established technique, currently attracting much interest across all fields of biophysics - especially with regard to enhanced focal resolution. The fundamental mechanism behind the technique, identified and understood through the application of quantum theory, reveals new optical polarization features that can be exploited to increase the information content of images from biological samples. In another development, based on a newly discovered, fundamentally related mechanism, it emerges the passage of off-resonant probe laser pulses may characteristically modify the intensity of single-photon fluorescence, and its associated optical polarization behavior. Here, the probe essentially confers optical nonlinearity on the decay transition, affording a means of optical control over the fluorescent emission. Compared to a catalogue of other laser-based techniques widely used in the life sciences, most suffer limitations reflecting the exploitation of specifically lifetime-associated features; the new optical control mechanism promises to be more generally applicable for the determination of kinetic data. Again, there is a prospect of improving spatial resolution, non-intrusively. It is anticipated that tight directionality can be imposed on single-photon fluorescence emission, expediting the development of new imaging applications. In addition, varying the optical frequency of the probe beam can add another dimension to the experimental parameter space. This affords a means of differentiating between molecular species with strongly overlapping fluorescence spectra, on the basis of their differential nonlinear optical properties. Such techniques significantly extend the scope and the precision of spatial and temporal information accessible from fluorescence studies.
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.
The theory of non-resonant optical processes with intrinsic optical nonlinearity, such as harmonic generation, has been widely understood since the advent of the laser. In general, such effects involve multiphoton interactions that change the population of each input optical mode or modes. However, nonlinear effects can also arise through the input of an off-resonant laser beam that itself emerges unchanged. Many such effects have been largely overlooked. Using a quantum electrodynamical framework, this review provides detail on such optically nonlinear mechanisms that allow for a controlled increase or decrease in the intensity of linear absorption and fluorescence and in the efficiency of resonance energy transfer. The rate modifications responsible for these effects were achieved by the simultaneous application of an off-resonant beam with a moderate intensity, acting in a sense as an optical catalyst, conferring a new dimension of optical nonlinearity upon photoactive materials. It is shown that, in certain configurations, these mechanisms provide the basis for all-optical switching, i.e., the control of light-by-light, including an optical transistor scheme. The conclusion outlines other recently proposed all-optical switching systems.
When fluorescence from electronically excited states follows the absorption of radiation, the emission spectrum is often a key to identification of the excited species. It now emerges that passing off-resonant laser light through such an electronically excited system may enhance or suppress the fluorescent emission. This report establishes the mechanism and theory for this optical control of spontaneous fluorescence, derived by quantum electrodynamical analysis. Experimental techniques to detect the enhanced signal are also proposed.