Radiative and non-radiative decay of a single molecule close to a metallic nanoparticle

We study the spontaneous emission of a single emitter close to a metallic nanoparticle, with the aim to clarify the distance dependence of the radiative and non-radiative decay rates. We derive analytical formulas based on a dipole-dipole model, and show that the non-radiative decay rate follows a R⁻⁶ dependence at short distance, where R is the distance between the emitter and the center of the nanoparticle, as in Förster’s energy transfer. The distance dependence of the radiative decay rate is more subtle. It is chiefly dominated by a R⁻³ dependence, a R⁻⁶ dependence being visible at plasmon resonance. The latter is a consequence of radiative damping in the effective dipole polarizability of the nanoparticle. The different distance behavior of the radiative and non-radiative decay rates implies that the apparent quantum yield always vanishes at short distance. Moreover, non-radiative decay is strongly enhanced when the emitter radiates at the plasmon-resonance frequency of the nanoparticle.     

Silver nanoparticle size–dependent measurement of quantum efficiency of Rhodamine 6G

The plasmonic absorption band of silver nanoparticles in the visible range of electromagnetic spectrum has been successfully exploited to alter the emission characteristics of the Rhodamine 6G dye molecule. The influence of the nanoparticle size on the fluorescence quantum yield of Rhodamine 6G is interrogated via steady state fluorescence as well as dual beam thermal lens technique. The potential of the thermal lens technique that probe nonradiative path in contrast to radiative path exhibited in the fluorescence spectra as a complementary method to measure the quantum yield of a dye molecule is exploited. Analysis of the results clearly indicates that the particle size and the spectral overlap between the emission spectra of Rhodamine 6G, and absorption spectra of the silver nanoparticles determine the quantum yield value of dye–nanoparticle mixture.     

Non-radiative decay of a dipole emitter close to a metallic nanoparticle: Importance of higher-order multipole contributions

The contribution of higher-order multipoles to radiative and non-radiative decay of a single dipole emitter close to a spherical metallic nanoparticle is re-examined. Taking a Ag spherical nanoparticle (AgNP) with the radius of 5 nm as an example, a significant contribution (between 50% and 101% of the total value) of higher-order multipoles to non-radiative rates is found even at the emitter distance of 5 nm from the AgNP surface. On the other hand, the higher-order multipole contribution to radiative rates is negligible. Consequently, a dipole-dipole approximation can yield only an upper bound on the apparent quantum yield. In contrast, the non-radiative rates calculated with the quasistatic Gersten and Nitzan method are found to be in much better agreement with exact electrodynamic results. Finally, the size corrected metal dielectric function is shown to decrease the non-radiative rates near the dipolar surface plasmon resonance.     

Spectrum of surface plasmons excited by spontaneous quantum dot transitions

We consider quantum fluctuations of near fields of a quantum emitter (two-level system (TLS) with population inversion sustained by incoherent pumping) in the near-field zone of a plasmon (metallic) nanoparticle. The spectrum of surface plasmons excited by spontaneous transitions in the quantum emitter is obtained below the lasing threshold of such a system (spaser) in the approximation of a small number of plasmons. It is shown that the relaxation rate is the sum of the quantum emitter’s rates of relaxation to its thermal reservoir and the plasmon cavity. The resulting dependence of the average number of plasmons on the pump intensity indicates the nonthreshold nature of the process.     

Distinguishing chemical and electromagnetic enhancement in surface‐enhanced Raman spectra: The case of para‐nitrothiophenol

Surface‐enhanced Raman spectra are simulated using a combined classical electrodynamics/real‐time time‐dependent density functional theory approach and compared to experiments. Emphasis is put on discerning between chemical and electromagnetic enhancement. Therefore, three different calculation scenarios are investigated using para‐nitrothiophenol as a test molecule. In the first one, corresponding to electromagnetic enhancement, we simulate the molecule alone with ab initio computations incorporating the electromagnetic field emitted by a nanoparticle. Chemical enhancement is modeled in the second scenario, where we include not only the molecule into the quantum chemistry calculations but also metal atoms of the nanoparticle. Here, any modification of the electromagnetic field due to the nanoparticle is not considered. In the third scenario, the former two setups are combined and demanding simulations of the hybrid system containing the molecule and the metal atoms exposed to a strongly modified electromagnetic field due to the plasmonic properties of the metallic nanoparticles are considered. Results are compared to our experimentally measured spectra. Based on our analysis, we show here on rigorous grounds that the electromagnetic effect leads to increased absolute Raman scattering cross sections but no change of the relative intensities. In contrast, the chemical effect leads to changes in relative peak height and also to newly emerging bands in the spectrum. These findings will have major implications in any study that concerns the interaction of molecules with metallic nanostructures. Copyright © 2013 John Wiley & Sons, Ltd.     

Size controlled synthesis of semiconductor nanocrystals in a continuous-flow mode microcapillary reactor

A microcapillary reactor with 320 μm inner diameter was utilized for CdSe nanoparticle synthesis. The influence of the reaction temperature and flow rate of precursors on the size and size distribution of prepared CdSe nanoparticles was systematically studied. The as-prepared nanoparticles exhibit sharp excitonic absorption and photoluminescence peak (FWHM 30 nm) with a quantum-yield around 10–40%. The microcapillary reactor was also used for CdSe/ZnS core-shell nanoparticle synthesis in continuous-flow mode. The quantum yield of the core-shell nanoparticles was found to be considerably influenced by the reactor temperature and have a close correlation with the thickness of ZnS shell under growth. An optimized quantum yield up to 70% was obtained for the CdSe/ZnS core-shell nanoparticles.     

Enhancement and quenching of single-molecule fluorescence

We present an experimental and theoretical study of the fluorescence rate of a single molecule as a function of its distance to a laser-irradiated gold nanoparticle. The local field enhancement leads to an increased excitation rate whereas nonradiative energy transfer to the particle leads to a decrease of the quantum yield (quenching). Because of these competing effects, previous experiments showed either fluorescence enhancement or fluorescence quenching. By varying the distance between molecule and particle we show the first experimental measurement demonstrating the continuous transition from fluorescence enhancement to fluorescence quenching. This transition cannot be explained by treating the particle as a polarizable sphere in the dipole approximation.     

Elastic rod model of a supercoiled DNA molecule

We study the elastic behaviour of a supercoiled DNA molecule. The simplest model is that of a rod-like chain, involving two elastic constants, the bending and the twist rigidities. Writing this model in terms of Euler angles, we show that the corresponding Hamiltonian is singular and needs a small distance cut-off, which is a natural length scale giving the limit of validity of the model, of the order of the double-helix pitch. The rod-like chain in the presence of the cut-off is able to reproduce quantitatively the experimentally observed effects of supercoiling on the elongation-force characteristics, in the small supercoiling regime. An exact solution of the model, using both transfer matrix techniques and its mapping to a quantum mechanics problem, allows to extract, from the experimental data, the value of the twist rigidity. We also analyse the variation of the torque and the writhe-to-twist ratio versus supercoiling, showing analytically the existence of a rather sharp crossover regime which can be related to the excitation of plectoneme-like structures. Finally we study the extension fluctuations of a stretched and supercoiled DNA molecule, both at fixed torque and at fixed supercoiling angle, and we compare the theoretical predictions to some preliminary experimental data. Received 1 April 1999 and Received in final form 4 January 2000     

The quantum yield of a metallic nanoantenna

The local-field factor and quantum yield of a metallic nanoantenna are studied to identify its enhancement of an emitter’s emission within the feed gap. For simplicity, a two-dimensional model, an Au nanoantenna with an emitter at the center, is studied. The electromagnetic field is solved by a set of surface integral equations. An incident plane wave irradiating the nanoantenna is modeled to simulate the excitation of the emitter by illuminating light, and the local-field factor is used to evaluate the amplification of the electric field in the feed gap of the metallic nanoantenna. Once the emitter becomes excited, a model of an electric dipole interacting with the nanoantenna is used for calculating the radiative and nonradiative powers to obtain the quantum yield of the excited emitter in the presence of the nanoantenna. The numerical results of quantum yield indicate that an Au nanoantenna acts as a low-pass filter for the emission of the emitter. Moreover, the smaller the feed gap, the larger the local-field factor but the less the quantum yield. PACS 78.67.-n; 33.80.-b; 33.50.-j; 42.30.-d; 42.50.Hz; 81.07.Pr     

Quantum plasmonics with quantum dot-metal nanoparticle molecules: influence of the Fano effect on photon statistics

We study theoretically the quantum optical properties of hybrid molecules composed of an individual quantum dot and a metallic nanoparticle. We calculate the resonance fluorescence of this composite system. Its incoherent part, arising from nonlinear quantum processes, is enhanced by more than 2 orders of magnitude as compared to that of the dot alone. The coupling between the two systems gives rise to a Fano interference effect which strongly influences the quantum statistical properties of the scattered photons: a small frequency shift of the incident light field may cause changes in the intensity correlation function of the scattered field of orders of magnitude. The system opens a good perspective for applications in active metamaterials and ultracompact single-photon devices.     

Relaxation of excited states of an emitter near a metal nanoparticle: An analysis based on superradiance theory

Methods of superradiance theory are employed for determining the relaxation rate of the excited state of a resonant emitter (atom, molecule, or quantum dot) near a metal nanoparticle under resonant excitation of plasmons in it, viz., modes of spatially uniform (dipole) harmonic oscillations of the electron density. Detuning from resonance and nonradiative loss suppressing radiation from the emitter near the nanoparticle surface are taken into account. The results are used to estimate the threshold conditions for generating a plasmon (“dipole”) nanolaser. It is shown that the threshold conditions of induced (laser) generation of plasmons for the emitter at a distance of 5–40 nm from an ellipsoidal nanoparticle are satisfied for relatively low emitter pumping rates (on the order of the rate of spontaneous emission of the emitter into the free space).     

A fractal model for heat transfer of nanofluids by convection in a pool

Based on the fractal distribution of nanoparticles, a fractal model for heat transfer of nanofluids is presented in the Letter. Considering heat convection between nanoparticles and liquids due to the Brownian motion of nanoparticles in fluids, the formula of calculating heat flux of nanofluids by convection is given. The proposed model is expressed as a function of the average size of nanoparticle, concentration of nanoparticle, fractal dimension of nanoparticle, temperature and properties of fluids. It is shown that the fractal model is effectual according to a good agreement between the model predictions and experimental data.     

Lattice contractions of a nanoparticle due to the surface tension: A model of elasticity

The lattice parameters of a metallic nanoparticle decrease with its size. To describe this phenomenon, a model based on elasticity is developed in this paper. Using this model, we investigate the lattice contraction of a metallic nanoparticle due to its surface tension. The effect of size-dependent surface tension on the lattice contraction is discussed. Furthermore, the lattice contraction of a nanoparticle of non-spherical shape is also approximately estimated by defining a shape factor. The analysis shows that the lattice parameters of metallic nanoparticle are size dependent. However, if the radius of nanoparticle is more than 5.0 nm, the effect of size on lattice contraction is almost negligible.     

The effect of randomly oriented anisotropy on the zero-field-cooled magnetization of a non-interacting magnetic nanoparticle assembly

A model based on localized partition function and master equation was set up to calculate the zero-field-cooled (ZFC) and field-cooled (FC) curves of a non-interacting magnetic nanoparticle assembly with randomly oriented anisotropy. The peak temperature of the ZFC curve corresponds to the highest energy barrier that acts against the unblocking process, and could be described well by an equation covering the heating rate effect. The predicted H^2/3 field dependence of the peak temperature is in good agreement with published results.     

Decay of a quantum dot in two-dimensional metallic photonic crystals

In this paper we have developed a theory for the decay of a quantum dot doped in a two-dimensional metallic photonic crystal consisting of two different metallic pillars in an air background medium. This crystal structure forms a full two-dimensional photonic band gap when the appropriate pillar sizes are chosen. The advantage of using two metals is that one can easily control the density of states and optical properties of these photonic crystals by changing the plasma energies of two metals rather than one. Using the Schrödinger equation method and the photonic density of states, we calculated the linewidth broadening and the spectral function of radiation due to spontaneous emission for two-level quantum dots doped in the system. Our results show that by changing the plasma energies one can control spontaneous emission of quantum dots doped in the metallic photonic crystal.     

Quantum size effects of CO reactivity on metallic quantum dots

We study the reactivity of a metallic quantum dot when exposed to a gas phase CO molecule. First, we perform a Newns-Anderson model calculation in which the valence electrons of the quantum dot are confined by a finite potential well and the molecule is characterized by its lowest unoccupied molecular orbital in the gas phase. A pronounced quantum size effect regarding the charge transfer between the quantum dot and molecule is observed. We then perform a first-principles calculation for a selected size interval. The quantum dot is described within the jellium model and the molecule by pseudopotentials. Our results show that the charge transfer between the quantum dot and the molecule depends critically on the size of the quantum dot, and that this dependence is intimately connected with the electronic structure. The key factor for charge transfer is the presence of states with the symmetry of the chemically active molecular orbital at the Fermi level.     

Theoretical studies of excitation dynamics in a peridinin-chlorophyll-protein coupled to a metallic nanoparticle

In this work we study the influence of plasmon excitations on the excitation dynamics within a protein complex embedding two chlorophyll molecules coupled to a gold nanosphere. Small separation between the chlorophylls and metallic nanoparticle allows us to simplify the calculations of the Förster energy transfer rate and non-radiative processes by replacing a spherical nanoparticle with a metallic surface. Our results show modifications of all relevant processes and the energy transfer pathways within the system as well as the radiative processes. Plasmon induced changes result in strong qualitative effects of the fluorescence of the studied light-harvesting complex.     

Plasmonic Dicke effect

We study cooperative emission by an ensemble of emitters, such as fluorescing molecules or semiconductor quantum dots, near a metal nanoparticle. The primary mechanism of cooperative emission is resonant energy transfer between emitters and plasmons rather than Dicke radiative coupling between emitters. The emission is dominated by three superradiant states with the same quantum yield as a single emitter, leading to a drastic reduction of ensemble radiated energy down to just thrice of that by a single emitter, the remaining energy being dissipated in the metal through subradiant states. We perform numerical calculations of system eigenstates and find that the plasmonic Dicke effect interactions affect is not impacted by the interactions between emitters or non-radiative losses in the metal.     

Efficient Population Transfer in a Λ-Type Quantum System Coupled to a Gold Nanoparticle Using STIRAP Shortcuts

A theoretical investigation on the population transfer in a Λ-type quantum system near a spherical gold nanoparticle under application of two stimulated Raman adiabatic passage (STIRAP) shortcuts and efficiency comparison with conventional STIRAP. It combines the density matrix approach for system dynamics, with classical electromagnetic calculations used to obtain the modified electric field amplitudes of the applied pulses and the Purcell factor of the quantum system due to the presence of the nanoparticle. The efficiency of population transfer is investigated by varying the distance between the quantum system and the nanoparticle, the free-space decay rate of quantum states, the mutual polarization, and the Rabi frequencies of each STIRAP shortcut pulses. In all cases, at least one of the applied shortcuts is more efficient than conventional STIRAP, while in most cases both perform better. When the pump and Stokes fields of the shortcuts have radial and tangential polarizations with respect to the nanoparticle surface, respectively, high transfer efficiency is obtained for small distances of the quantum system to the nanoparticle, moderate free space decay rates and large Rabi frequencies of the fields, while when the pulse polarizations are interchanged, the transfer becomes highly efficient only at large distances.