Sergey Polyutov

Suppression of surface plasmon resonance in Au nanoparticles upon transition to the liquid state.

Significant suppression of resonant properties of single gold nanoparticles at the surface plasmon frequency during heating and subsequent transition to the liquid state has been demonstrated experimentally and explained for the first time. The results for plasmonic absorption of the nanoparticles have been analyzed by means of Mie theory using experimental values of the optical constants for the liquid and solid metal. The good qualitative agreement between calculated and experimental spectra support the idea that the process of melting is accompanied by an abrupt increase of the relaxation constants, which depends, beside electron-phonon coupling, on electron scattering at a rising number of lattice defects in a particle upon growth of its temperature, and subsequent melting as a major cause for the observed plasmonic suppression. It is emphasized that observed effect is fully reversible and may underlie nonlinear optical responses of nanocolloids and composite materials containing plasmonic nanoparticles and their aggregates in conditions of local heating and in general, manifest itself in a wide range of plasmonics phenomena associated with strong heating of nanoparticles.

Gradual collapse of nuclear wave functions regulated by frequency tuned X-ray scattering

As is well established, the symmetry breaking by isotope substitution in the water molecule results in localisation of the vibrations along one of the two bonds in the ground state. In this study we find that this localisation may be broken in excited electronic states. Contrary to the ground state, the stretching vibrations of HDO are delocalised in the bound core-excited state in spite of the mass difference between hydrogen and deuterium. The reason for this effect can be traced to the narrow “canyon-like” shape of the potential of the state along the symmetric stretching mode, which dominates over the localisation mass-difference effect. In contrast, the localisation of nuclear motion to one of the HDO bonds is preserved in the dissociative core-excited state . The dynamics of the delocalisation of nuclear motion in these core-excited states is studied using resonant inelastic X-ray scattering of the vibrationally excited HDO molecule. The results shed light on the process of a wave function collapse. After core-excitation into the state of HDO the initial wave packet collapses gradually, rather than instantaneously, to a single vibrational eigenstate.

Thermal effects in systems of colloidal plasmonic nanoparticles in high-intensity pulsed laser fields [Invited]

We have studied light induced processes in nanocolloids and composite materials containing ordered and disordered aggregates of plasmonic nanoparticles accompanied by their strong heating. A universal comprehensive physical model that combines mechanical, electrodynamical, and thermal interactions at nanoscale has been developed as a tool for investigations. This model was used to gain deep insight on phenomena that take place in nanoparticle aggregates under high-intensity pulsed laser radiation resulting in the suppression of nanoparticle resonant properties. Verification of the model was carried out with single colloidal Au and Ag nanoparticles and their aggregates.

Bidirectional description of amplified spontaneous emission induced by three-photon absorption

A semiclassical dynamic theory of the nonlinear propagation of a few interacting intense light pulses is applied to study the nonlinear counterpropagation of amplified spontaneous emission (ASE) induced by three-photon absorption of short intense laser pulses in a chromophore solution. Several important results from the modeling are reached for the ASE process developing in the regime of strong saturation. Accounting for ASE in both forward and backward directions with respect to the pump pulse results in a smaller efficiency of nonlinear conversion for the forward ASE compared with the case in which forward emission is considered alone, something that results from the partial repump of the absorbed energy to the backward ASE component; the overall efficiency is nevertheless higher than for the forward emission considered alone. The efficiency of nonlinear conversion of the pump energy to the counterpropagating ASE pulses is strongly dependent on the concentration of active molecules so that a particular combination of concentration versus cell length optimizes the conversion coefficient. Under certain specified conditions, the ASE effect is found to be oscillatory; the origin of oscillations is dynamical competition between stimulated emission and off-resonant absorption. This result can be considered one of the possible explanations of the temporal fluctuations of the forward ASE pulse [Nature 415, 767 (2002)].

Refractory titanium nitride two-dimensional structures with extremely narrow surface lattice resonances at telecommunication wavelengths

Regular arrays of plasmonic nanoparticles have brought significant attention over the last decade due to their ability to support localized surface plasmons (LSPs) and exhibit diffractive grating behavior simultaneously. For a specific set of parameters (i.e., period, particle shape, size, and material), it is possible to generate super-narrow surface lattice resonances (SLRs) that are caused by interference of the LSP and the grating Rayleigh anomaly. In this letter, we propose plasmonic structures based on regular 2D arrays of TiN nanodisks to generate high-Q SLRs in an important telecommunication range, which is quite difficult to achieve with conventional plasmonic materials. The position of the SLR peak can be tailored within the whole telecommunication bandwidth (from ≈ 1.26 μm to ≈ 1.62 μm) by varying the lattice period, while the Q-factor is controlled by changing nanodisk sizes. We show that the Q-factor of SLRs can reach a value of 2 × 103, which is the highest reported Q-factor for SLRs at tele...

Biphasic aggregation of a perylene bisimide dye identified by exciton-vibrational spectra

The quantum efficiency of light emission is a crucial parameter of supramolecular aggregates that can be tuned by the molecular design of the monomeric species. Here, we report on a strong variation of the fluorescence quantum yield due to different phases of aggregation for the case of a perylene bisimide dye. In particular, a change of the dominant aggregation character from H- to J-type within the first aggregation steps is found, explaining the observed dramatic change in quantum yield. This behaviour is rationalised by means of a systematic study of the intermolecular potential energy surfaces using the time-dependent density functional based tight-binding (TD-DFTB) method. This provides a correlation between structural changes and a coupling strength and supports the notion of H-type stacked dimers and J-type stack-slipped dimers. The exciton-vibrational level structure is modelled by means of an excitonic dimer model including two effective vibrational modes per monomer. Calculated absorption and fluorescence spectra are found to be in reasonable agreement with experimental ones, thus supporting the conclusion on the aggregation behaviour.

Optimization of photothermal methods for laser hyperthermia of malignant cells using bioconjugates of gold nanoparticles

Selective action of laser radiation on membranes of malignant cells has been studied in different regimes using conjugates of gold nanoparticles with oligonucleotides by the example of DNA aptamers. Under the conditions of a contact between a bioconjugate and a cell surface and the development of substantial and rapidly relaxing temperature gradients near a nanoparticle, the membranes of malignant cells alone are efficiently damaged due to the local hyperthermia of a cellular membrane. It has been shown that employment of pulsed instead of continuous wave laser radiation provides the localization of the damaging action, which does not involve healthy cells.

Thermal limiting effects in optical plasmonic waveguides

Abstract We have studied thermal effects occurring during excitation of optical plasmonic waveguide (OPW) in the form of linear chain of spherical Ag nanoparticles by pulsed laser radiation. It was shown that heating and subsequent melting of the first irradiated particle in a chain can significantly deteriorate the transmission efficiency of OPW that is the crucial and limiting factor and continuous operation of OPW requires cooling devices. This effect is caused by suppression of particles surface plasmon resonance due to reaching the melting point temperature. We have determined optimal excitation parameters which do not significantly affect the transmission efficiency of OPW.

Far-Zone Resonant Energy Transfer in X-ray Photoemission as a Structure Determination Tool

Near-zone Förster resonant energy transfer is the main effect responsible for excitation energy flow in the optical region and is frequently used to obtain structural information. In the hard X-ray region, the Förster law is inadequate because the wavelength is generally shorter than the distance between donors and acceptors; hence, far-zone resonant energy transfer (FZRET) becomes dominant. We demonstrate the characteristics of X-ray FZRET and its fundamental differences with the ordinary near-zone resonant energy-transfer process in the optical region by recording and analyzing two qualitatively different systems: high-density CuO polycrystalline powder and SF6 diluted gas. We suggest a method to estimate geometrical structure using X-ray FZRET employing as a ruler the distance-dependent shift of the acceptor core ionization potential induced by the Coulomb field of the core-ionized donor.

Restructuring of plasmonic nanoparticle aggregates with arbitrary particle size distribution in pulsed laser fields

We have studied processes of interaction of pulsed laser radiation with resonant groups of plasmonic nanoparticles (resonant domains) in large colloidal nanoparticle aggregates having different interparticle gaps and particle size distributions. These processes are responsible for the origin of nonlinear optical effects and photochromic reactions in multiparticle aggregates. To describe photo-induced transformations in resonant domains and alterations in their absorption spectra remaining after the pulse action, we introduce the factor of spectral photomodification. Based on calculation of changes in thermodynamic, mechanical, and optical characteristics of the domains, the histograms of the spectrum photomodification factor have been obtained for various interparticle gaps, an average particle size, and the degree of polydispersity. Variations in spectra have been analyzed depending on the intensity of laser radiation and various combinations of size characteristics of domains. The obtained results can be used to predict manifestation of photochromic effects in composite materials containing different plasmonic nanoparticle aggregates in pulsed laser fields.