Plexciton quenching by resonant electron transfer from quantum emitter to metallic nanoantenna.

Coupling molecular excitons and localized surface plasmons in hybrid nanostructures leads to appealing, tunable optical properties. In this respect, the knowledge about the excitation dynamics of a quantum emitter close to a plasmonic nanoantenna is of importance from fundamental and practical points of view. We address here the effect of the excited electron tunneling from the emitter into a metallic nanoparticle(s) in the optical response. When close to a plasmonic nanoparticle, the excited state localized on a quantum emitter becomes short-lived because of the electronic coupling with metal conduction band states. We show that as a consequence, the characteristic features associated with the quantum emitter disappear from the optical absorption spectrum. Thus, for the hybrid nanostructure studied here and comprising quantum emitter in the narrow gap of a plasmonic dimer nanoantenna, the quantum tunneling might quench the plexcitonic states. Under certain conditions the optical response of the system approaches that of the individual plasmonic dimer. Excitation decay via resonant electron transfer can play an important role in many situations of interest such as in surface-enhanced spectroscopies, photovoltaics, catalysis, or quantum information, among others.

Quantum plasmonics: nonlinear effects in the field enhancement of a plasmonic nanoparticle dimer.

A fully quantum mechanical investigation using time-dependent density functional theory reveals that the field enhancement in a coupled nanoparticle dimer can be strongly affected by nonlinear effects. We show that both classical as well as linear quantum mechanical descriptions of the system fail even for moderate incident light intensities. An interparticle current resulting from the strong field photoemission tends to neutralize the plasmon-induced surface charge densities on the opposite sides of the nanoparticle junction. Thus, the coupling between the two nanoparticles and the field enhancement is reduced as compared to linear theory. A substantial nonlinear effect is revealed already at incident powers of 10(9) W/cm(2) for interparticle separation distances as large as 1 nm and down to the touching limit.

Bound States in the continuum in photonics.

With examples of two parallel dielectric gratings and two arrays of thin parallel dielectric cylinders, it is shown that the interaction between trapped electromagnetic modes can lead to scattering resonances with practically zero width. Such resonances are the bound states in the radiation continuum first discovered in quantum systems by von Neumann and Wigner. Potential applications of such photonic systems include: large amplification of electromagnetic fields within photonic structures and, hence, enhancement of nonlinear phenomena, biosensing, as well as perfect filters and waveguides for a particular frequency, and impurity detection.

Resonant infrared multiphoton dissociation spectroscopy of gas-phase protonated peptides. Experiments and Car-Parrinello dynamics at 300 K.

The gas-phase structures of protonated peptides are studied by means of resonant infrared multiphoton dissociation spectroscopy (R-IRMPD) performed with a free electron laser. The peptide structures and protonation sites are obtained through comparison between experimental IR spectra and their prediction from quantum chemistry calculations. Two different analyses are conducted. It is first supposed that only well-defined conformations, sufficiently populated according to a Boltzmann distribution, contribute to the observed spectra. On the contrary, DFT-based Car-Parrinello molecular dynamics simulations show that at 300 K protonated peptides no longer possess well-defined structures, but rather dynamically explore the set of conformations considered in the first conventional approach.

Ab initio molecular dynamics of protonated dialanine and comparison to infrared multiphoton dissociation experiments.

Finite temperature Car-Parrinello molecular dynamics simulations are performed for the protonated dialanine peptide in vacuo, in relation to infrared multiphoton dissociation experiments. The simulations emphasize the flexibility of the different torsional angles at room temperature and the dynamical exchange between different conformers which were previously identified as stable at 0 K. A proton transfer occurring spontaneously at the N-terminal side is also observed and characterized. The theoretical infrared absorption spectrum is computed from the dipole time correlation function, and, in contrast to traditional static electronic structure calculations, it accounts directly for anharmonic and finite temperature effects. The comparison to the experimental infrared multiphoton dissociation spectrum turns out very good in terms of both band positions and band shapes. It does help the identification of a predominant conformer and the attribution of the different bands. The synergy shown between the experimental and theoretical approaches opens the door to the study of the vibrational properties of complex and floppy biomolecules in the gas phase at finite temperature.

Effect of an atomically thin dielectric film on the surface electron dynamics: image-potential states in the Ar/Cu(100) system.

The effect of an atomically thin Ar layer on the image-potential states on Cu(100) surfaces is studied in a joint experimental-theoretical study, allowing a detailed analysis of the interaction between a surface electron and a thin insulator layer. A microscopic theoretical description of the Ar layer is developed based on mutually polarizing Ar atoms. Account of the 3D Ar layer structure allows one to predict energies and lifetimes of the image states in excellent agreement with the observations. The Ar layer, even as thin as one monolayer, is efficiently insulating the state from the metal.