Nonradiative and radiative Förster energy transfer between quantum dots

We theoretically study nonradiative and radiative energy transfer between two localized quantum emitters, a donor (initially excited) and an acceptor (receiving the excitation). The rates of nonradiative and radiative processes are calculated depending on the spatial and spectral separation between the donor and acceptor states and for different donor and acceptor lifetimes for typical parameters of semiconductor quantum dots. We find that the donor lifetime can be significantly modified only due to the nonradiative Förster energy transfer process at donor–acceptor separations of approximately 10 nm (depending on the acceptor radiative lifetime) and for the energy detuning not larger than 1–2 meV. The efficiency of the nonradiative Förster energy transfer process under these conditions is close to unity and decreases rapidly with an increase in the donor–acceptor distance or energy detuning. At large donor–acceptor separations greater than 40 nm, the radiative corrections to the donor lifetime are comparable with nonradiative ones but are relatively weak.     

Excitons in molecular J-aggregates of cyanine dyes: Simulation of trapping and energy transfer

A theoretical model is provided to simulate the energy transfer and trapping of excitons in cyanine J-aggregates for various geometrical configurations. Intermolecular interactions are calculated using the extended dipole method. Frenkel exciton states are obtained by a numerical diagonalization of the aggregate Hamiltonian taking into account the static disorder. A model of exciton–phonon coupling is used to describe the trapping and the energy transfer processes among the exciton states. Scattering rates are calculated and used in a Master Equation to obtain the time evolution of the excitonic populations after initial excitation. Configurationally averaged absorption lineshapes and time-resolved fluorescence decays are obtained. Our simulation model is applied to describe the excitation energy transfer between two closely spaced linear chains of pseudoisocyanine (PIC) molecules and to a two-dimensional monolayer composed of a mixing of oxacyanine and thiacyanine molecules.     

Influence of Mg Composition on Optical Properties of Exciton Confinement in Strained Wurtzite ZnO/MgxZn1-xO Cylindrical Quantum Dots

Based on the effective-mass approximation and variational approach, excitonic optical properties are investigated theoretically in strained wurtzite (WZ) ZnO/Mg_xZn_1-xO cylindrical quantum dots (QDs) for four different Mg compositions: x=0.08, 0.14, 0.25, and 0.33, with considering a three-dimensional carrier confinement in QDs and a strong built-in electric field effect due to the piezoelectricity and spontaneous polarization. The ground-state exciton binding energy, the interband emission wavelength, and the radiative lifetime as functions of the QD structural parameters (height and radius) are calculated in detail. The computations are performed in the case of finite band offset. Numerical results elucidate that Mg composition has a significant influence on the exciton states and optical properties of ZnO/Mg_xZn_1-xO QDs. The ground-state exciton binding energy increases with increasing Mg composition and the increment tendency is more prominent for small height QDs. As Mg composition increases, the interband emission wavelength has a blue-shift if the dot height L<3.5 nm, but the interband emission wavelength has a red-shift when L>3.5 nm. Furthermore, the radiative lifetime increases rapidly with increasing Mg composition if the dot height L>3 nm and the increment tendency is more prominent for large height QDs. The physical reason has been analyzed in depth.     

Influence of Mg Composition on Optical Properties of Exciton Confinement in Strained Wurtzite ZnO/Mg_x Zn_(1-x) O Cylindrical Quantum Dots

Based on the effective-mass approximation and variational approach, excitonic optical properties are investigated theoretically in strained wurtzite (WZ) ZnO/Mg x Zn 1-x O cylindrical quantum dots (QDs) for four different Mg compositions: x = 0.08, 0.14, 0.25, and 0.33, with considering a three-dimensional carrier confinement in QDs and a strong built-in electric field effect due to the piezoelectricity and spontaneous polarization. The ground-state exciton binding energy, the interband emission wavelength, and the radiative lifetime as functions of the QD structural parameters (height and radius) are calculated in detail. The computations are performed in the case of finite band offset. Numerical results elucidate that Mg composition has a significant influence on the exciton states and optical properties of ZnO/Mg x Zn 1 x O QDs. The ground-state exciton binding energy increases with increasing Mg composition and the increment tendency is more prominent for small height QDs. As Mg composition increases, the interband emission wavelength has a blue-shift if the dot height L 3.5 nm, but the interband emission wavelength has a red-shift when L 3.5 nm. Furthermore, the radiative lifetime increases rapidly with increasing Mg composition if the dot height L 3 nm and the increment tendency is more prominent for large height QDs. The physical reason has been analyzed in depth.     

Energy transfer between two aggregates in light-harvesting complexes

Energy transfer processes between two aggregates in a coupled chromophoric-pigment(protein)system are studied via the standard master equation approach.Each pigment of the two aggregates is modeled as a two-level system.The excitation energy is assumed to be transferred from the donor aggregate to the acceptor aggregate.The model can be used to theoretically simulate many aspects of light-harvesting complexes(LHCs).By applying the real bio-parameters of photosynthesis,we numerically investigate the efficiency of energy transfer(EET)between the two aggregates in terms of some factors,e.g.,the initial coherence of the donor aggregate,the coupling strengthes between the two aggregates and between different pigments,and the effects of noise from the environment.Our results provide evidence for that the actual numbers of pigments in the chromophoric rings of LHCs should be the optimum parameters for a high EET.We also give a detailed analysis of the effects of noise on the EET.     

Spin polarization transfer during intramolecular triplet-triplet energy transfer as studied by time resolved EPR spectroscopy

Spin polarization conservation during intramolecular triplet-triplet energy transfer was studied for the phthalimide derivatives. It is shown that spin polarization transfer is useful for determining the conformation and the nature of the lowest triple (T₁) states of the donor and acceptor moieties. The polarization pattern of the acceptor triplet state was well reproduced taking into account the polarization of the donor and the mutual orientation of the donor and acceptor moieties. This technique clarified the order of the triplet sublevels in energy of the phthalimide chromophore. The T₁ states of stilbene derivatives, which have a low quantum yield of intersystem crossing under direct excitation, were also detected.     

聚二甲基硅氧烷微流道中光流控荧光共振能量转移激光

将单一折射率的石英裸光纤植入由聚二甲基硅氧烷构成的基片微流道中,以低折射率的罗丹明B(RhB)和吡啶821(LDS821)乙醇溶液构成的供体和受体对作为激光增益介质.采用沿光纤轴向消逝波抽运方式,首先以波长为532nm的连续波激光器作为激励光,对荧光共振能量转移特性参数进行了研究.然后以波长为532nm的脉冲激光器作为抽运光,通过直接激励供体分子RhB,并将其能量转移给临近的受体分子LDS821,在不改变抽运光波长的条件下,实现了较低阈值(1.26μJ/mm~2)的受体LDS821激光辐射.     

Two-photon absorption in the vicinity of the exciton absorption in CdS

The two-photon absorption spectrum of CdS in the wavelength region of the free and bound exciton lines has been measured using a pulsed dye laser and a differential transmittance technique. An intense absorption band is observed which is possibly due to the interference of the contributions of different intermediate states to the interband two-photon absorption. No absorption is observed which can be attributed to the formation of free excitonic molecules.     

All-optical switching between quantum dot nanoarrays

An all-optical switching device is proposed, based on a sandwich structure comprising two-dimensional square-lattice nanoarrays of donor and acceptor quantum dots. The system operates on Förster energy transfer between the dark states of the individual nanoparticles, normally precluded by selection rules. On application of an off-resonant laser beam, a nonlinear mechanism activates transfer between spatially correlated quantum dots across an optically passive spacer layer, signifying an active switching action with parallel processing capability. In this report, electrodynamic theory is employed to analyse the system and to evaluate its energy transfer fidelity. The results of model calculations are presented in graphical form.     

Electroreflectance of bound excitonic states in semiconductors

While first-derivative spectroscopy (thermoreflectance, piezoreflectance, wavelength derivative modulation) has a general validity, no matter whether one is studying interband or excitonic transitions (involving also bound states), things are more complex in the case of electroreflectance (ER). As a matter of fact, Aspnes and Rowe's third-derivative theory does not include bound excitonic states. Using a phenomenological approach one can see that only in the case of a strong mixing between d³ε_r/dE³ and d³ε₁/dE³ it is possible to observe a qualitative agreement between Δε and d³ε/dE³ in some particular cases where Wannier excitonic series gives a predominant contribution to the optical spectra.     

Theoretical studies of polarization dependent electro-optical modulation in lattice matched and strained multi-quantum well structures

We report on polarization dependent optical absorption for excitonic and interband transitions in lattice matched (GaAs/AlGaAs) and strained (biaxial tensile strain - GaAsP/AlGaAs; biaxial compressive strain - InGaAs/AlGaAs) multiquantum well structures in the presence of transverse electric fields. The hole states are solved by using the Kohn-Luttinger Hamiltonian and using an eigenvalue technique. The effect of heavy-hole and light-hole mixing due to the strain, electric field and quantization is studied. Under biaxial tensile strain the heavy-hole and light-hole transition can coincide, leading to interesting polarization dependent effects. Results are presented for excitonic and interband transitions.     

Energy transfer in solid-state dye lasers based on methyl methacrylate co-doped with sulforhodamine B and crystal violet

Laser action in methyl methacrylate(MMA)co-doped with sulforhodamine B and crystal violet dyes was investigated.The dye mixture was incorporated into a solid polymeric matrix and was pumped by a 532-nm Nd:YAG laser.Distributed feedback dye laser(DFDL)action was induced in the dye mixture using a prism arrangement both in the donor and acceptor regions by an energy transfer mechanism.Theoretically,the characteristics of acceptor and donor DFDLs,and the dependence of their pulse widths and output powers on acceptor–donor concentrations and pump power,were studied.Experimentally,the output energy of DFDL was measured at the emission peaks of donor and acceptor dyes for different pump powers and different acceptor–donor concentrations.Tuning of the output wavelength was achieved by varying the period of the gain modulation of the laser medium.The laser wavelength showed continuous tunability from 563 nm to648 nm.     

Terbium(III) Chelate as an Efficient Donor for Multiple-Wavelength Fluorescent Acceptors

The emission spectra of the lanthanide chelates enable them to act as a donor for several acceptors emitting at different wavelengths. Fluorescence resonance energy transfer between terbium(III) chelate labeled antibody Fab fragment (donor) and a 17β-estradiol conjugated to Alexa Fluor 488, 555, 594 or 680 (acceptor) was employed to study the functionality of the terbium(III) chelate as an efficient donor for several acceptors emitting from green to far-red. During measurement, the sensitized emission of the acceptor was measured at acceptor specific wavelength. All the tested dyes proved to be efficient acceptors, and they were successfully used in the competitive homogeneous E2 assay. The highest signal to background ratio and the best assay performance was obtained with Alexa Fluor 680, due to the very low donor emission background at the far-red area. In addition, the sensitized emission of both Alexa Fluor 488 and 680 could be measured simultaneously without significant cross talk.     

A Theory of Electronic Energy Transfer in Complex Molecular Systems

The Förster theory for energy transfer is critically reviewed in the context of the present-day theory of nonradiative transitions, and the fundamental tenets of the Förster theory are shown to be erroneous. A new theory of electronic energy transfer is constructed taking into account the electronic transition theory. The intermolecular interaction between donor and acceptor molecules is assumed to perturb electron states of isolated molecules before the donor-molecule excitation. A distinguishing characteristic of the intermolecular interaction is spatial delocalization of the wave functions of electron states of the interacting molecules. It is this fact that has made it possible to realize ordinary photophysical processes between electron states of various molecules in a bimolecular system. In the experiments under study, the result of the intermolecular nonradiative photoprocess is given as evidence of electronic energy transfer from the donor molecule to the acceptor molecule.     

Effect of VI/II ratio upon photoluminescence properties of aluminum-doped ZnTe layers grown by MOVPE

The photoluminescence properties of aluminum (Al)-doped ZnTe layers grown by atmospheric pressure metalorganic vapor phase epitaxy have been investigated as a function of the ratio of transport rate of diethyltelluride and dimethyl (VI/II ratio). When VI/II ratio is increased, the excitonic emission and donor–acceptor pair emission due to Al donor become predominantly in the spectrum of ZnTe layer. This suggests that Al is effectively incorporated into ZnTe. Several bound excitonic emissions associated with residual acceptor impurities are also detected in the spectrum together with free excitonic emission. When VI/II ratio exceeds 3, the deep level emission associated with the complex of Al donor and Zn vacancy which roles the acceptor for ZnTe are induced. It seems that the intensity of this emission band is independent of dopant transport rate.     

Energy transfer between fluorescent dyes in photonic crystals

Energy transfer from fluorescein (Fl) to Rhodamine B (RhB) in the opal photonic crystals has been investigated by photoluminescence. The results show that the energy transfer can be enhanced effectively by photonic bandgaps. When the fluorescence emission wavelength of donor Fl overlaps the photonic bandgap the fluorescence intensity of the donor is suppressed, while the fluorescence intensity of acceptor RhB is obviously enhanced. This enhancement can be attributed to the inhibition of radiative emission of the donor in the photonic crystals.     

Determination of the Efficiency and Energy Transfer Rate in the Fluorescence of a Single Donor–Acceptor Pair Attached to a Biomolecule

Resonance energy transfer from a single donor molecule to a single acceptor molecule (Förster resonance energy transfer) is currently used to determine the microscopic parameters describing interconformational changes in a protein molecule to which this single donor–acceptor pair is attached. A recently developed method makes it possible to intricately search for such parameters using a formula for the efficiency of Förster resonance energy transfer, which is the sum of several Gaussians. Another simpler method for the determination of the desired parameters of interconformational transitions has been proposed in this work on the basis of statistical processing of fluctuating tracks of fluorescence of a single donor–acceptor pair attached to a protein molecule.     

Electronic States and Photoprocesses in Bichromophore Systems

We present the results of quantumchemical investigation of energy transfer in organic molecules and systems and the inferences drawn. The Förster theory has been subjected to a critical analysis in order that the energy transfer could be described in the context of the current theory of nonradiative transitions and the incorrectness of the basic premises of the Förster theory has been demonstrated. A new variant of the mechanism of electronic energy transfer on the basis of the theory of electron transitions and of the quantum mechanics of molecules has been suggested. It is shown that the interaction of the molecules of the donor and acceptor perturbs the electronic states of isolated molecules even before the excitation of the donor molecule. A characteristic feature of the manifestation of intermolecular interaction is the spatial delocalization of the wave functions of the electronic states of interacting molecules, leading to the possibility of occurrence of conventional photophysical processes with participation of the electronic states of various molecules of the bimolecular system. In experimental investigations, the result of the intermolecular nonradiative transition is recorded as evidence of the spatial transfer of the energy of electronic excitation from the donor molecule to the acceptor molecule.     

Enhanced Emission Induced by FRET from a Long-Lifetime, Low Quantum Yield Donor to a Long-Wavelength, High Quantum Yield Acceptor

We report observation of high quantum yield, long-lifetime fluorescence from a red dye BO-PRO-3 excited by resonance energy transfer (RET). The acceptor fluorescence was highly enhanced upon binding to the donor-labeled DNA. A ruthenium complex (Ru) was chosen as a donor in this system because of its long fluorescence lifetime. Both donor and acceptor were non-covalently bound to DNA. Emission from the donor-acceptor system (DA) at wavelengths exceeding 600 nm still preserves the long-lifetime component of the Ru donor, retaining average fluorescence lifetimes in the range of 30–50 ns. Despite the low quantum yield of the Ru donor in the absence of acceptor, its overall quantum yield of the DA pair was increased by energy transfer to the higher quantum yield acceptor BO-PRO-3. The wavelength-integrated intensity of donor and acceptor bound to DNA was many-fold greater than the intensity of the donor and acceptor separately bound to DNA. The origin of this effect is due to an efficient energy transfer from the donor, competing with non-radiative depopulation of the donor excited state. The distinctive features of DA complexes can be used in the development of a new class of engineered luminophores that display both long lifetime and long-wavelength emission. Similar DA complexes can be applied as proximity indicators, exhibiting strong fluorescence of adjacently located donors and acceptors over the relatively weak fluorescence of separated donors and acceptors.