Fluorescence quenching near small metal nanoparticles

We develop a microscopic model for fluorescence of a molecule (or semiconductor quantum dot) near a small metal nanoparticle. When a molecule is situated close to metal surface, its fluorescence is quenched due to energy transfer to the metal. We perform quantum-mechanical calculations of energy transfer rates for nanometer-sized Au nanoparticles and find that non-local and quantum-size effects significantly enhance dissipation in metal as compared to those predicted by semiclassical electromagnetic models. However, the dependence of transfer rates on molecule's distance to metal nanoparticle surface, $d$, is significantly weaker than the $d^{-4}$ behavior for flat metal surface with a sharp boundary predicted by previous calculations within random phase approximation.Comment: 7 pages, 5 figure

Kinetics of the Photoreduction of \u3cem\u3ep\u3c/em\u3e-nitrobenzoic Acid on Ag and AgxAu1-x Nanoparticle Films

A recent strategy to increase the efficiency of photovoltaic and photoemissive devices has been to include metal nanolayers in contact with an organic layer inside these devices. Metal nanoparticles (especially Ag and Au) are known to catalyze photoreactions of organic molecules on their surfaces. The reactivity of organics at nanometal surfaces has implications for device lifetimes; therefore, it is important to understand how nanoparticle size and composition influence reaction rates. The photoreduction of p-nitrobenzoate (PNBA) to p,p’-azodibenzoate (PPADBA) on Ag nanoparticles is an excellent model system for studying such reactions. We have measured the reaction rate of PNBA to PPADBA on Ag and Au based nanoparticle surfaces using surface-enhanced Raman spectroscopy (SERS). SERS is a highly sensitive spectroscopic tool, which provides molecular fingerprints that can be used to identify molecular species present on metal nanoparticle surfaces. These surfaces are made from layers from Ag and AgxAu1-x alloy nanoparticles with diameters ranging from 50-80 nm

Microscopic theory of single-electron tunneling through molecular-assembled metallic nanoparticles

We present a microscopic theory of single-electron tunneling through metallic nanoparticles connected to the electrodes through molecular bridges. It combines the theory of electron transport through molecular junctions with the description of the charging dynamics on the nanoparticles. We apply the theory to study single-electron tunneling through a gold nanoparticle connected to the gold electrodes through two representative benzene-based molecules. We calculate the background charge on the nanoparticle induced by the charge transfer between the nanoparticle and linker molecules, the capacitance and resistance of molecular junction using a first-principles based Non-Equilibrium Green's Function theory. We demonstrate the variety of transport characteristics that can be achieved through ``engineering'' of the metal-molecule interaction.Comment: To appear in Phys. Rev.

Plasmon-assisted two-photon Rabi oscillations in a semiconductor quantum dot -- metal nanoparticle heterodimer

Tho-photon Rabi oscillations hold potential for quantum computing and quantum information processing, because during a Rabi cycle a pair of entangled photons may be created. We theoretically investigate the onset of this phenomenon in a heterodimer comprising a semiconductor quantum dot strongly coupled to a metal nanoparticle. Two-photon Rabi oscillations in this system occur due to a coherent two-photon process involving the ground-to-biexciton transition in the quantum dot. The presence of a metal nanoparticle nearby the quantum dot results in a self-action of the quantum dot via the metal nanoparticle, because the polatization state of the latter depends on the quantum state of the former. The interparticle interaction gives rise to two principal effects: (i) - enhancement of the external field amplitude and (ii) - renormalization of the quantum dot's resonance frequencies and relaxation rates of the off-diagonal density matrix elements, both depending on the populations of the quantum dot's levels. Here, we focus on the first effect, which results in interesting new features, in particular, in an increased number of Rabi cycles per pulse as compared to an isolated quantum dot and subsequent growth of the number of entangled photon pairs per pulse. We also discuss the destructive role of radiative decay of the excitonic states on two-photon Rabi oscillations for both an isolated quantum dot and a heterodimer.Comment: 11 pages, 19 figure

Nonlinear metal-dielectric nanoantennas for light switching and routing

We introduce a novel hybrid metal-dielectric nanoantenna composed of dielectric (crystalline silicon) and metal (silver) nanoparticles. A high-permittivity dielectric nanoparticle allows to achieve effective light harvesting, and nonlinearity of a metal nanoparticle controls the radiation direction. We show that the radiation pattern of such a nanoantenna can be switched between the forward and backward directions by varying only the light intensity around the level of 11 MW/cm$^2$, with the characteristic switching time of 260 fs.Comment: 9 pages, 5 figures, submitted to New J. Phy

Size-dependent Correlation Effects in Ultrafast Optical Dynamics of Metal Nanoparticles

We study the role of collective surface excitations in the electron relaxation in small metal particles. We show that the dynamically screened electron-electron interaction in a nanoparticle contains a size-dependent correction induced by the surface. This leads to new channels of quasiparticle scattering accompanied by the emission of surface collective excitations. We calculate the energy and temperature dependence of the corresponding rates, which depend strongly on the nanoparticle size. We show that the surface-plasmon-mediated scattering rate of a conduction electron increases with energy, in contrast to that mediated by a bulk plasmon. In noble-metal particles, we find that the dipole collective excitations (surface plasmons) mediate a resonant scattering of d-holes to the conduction band. We study the role of the latter effect in the ultrafast optical dynamics of small nanoparticles and show that, with decreasing nanoparticle size, it leads to a drastic change in the differential absorption lineshape and a strong frequency dependence of the relaxation near the surface plasmon resonance. The experimental implications of our results in ultrafast pump-probe spectroscopy are also discussed.Comment: 29 pages including 6 figure