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The dependence of plasmon resonance excitations in ultrafine (3-7 nm) gold nanoparticles on heating and melting is investigated. An integrated approach is adopted, where molecular dynamics simulations of the spatial and temporal development of the atoms constituting the nanoparticles generate trajectories out of which system conformations are sampled and extracted for calculations of plasmonic excitation cross sections which then are averaged over the sample configurations for the final result. The calculations of the plasmonic excitations, which take into account the temperature- and size-dependent relaxation of the plasmons, are carried out with a newly developed Extended Discrete Interaction Model (Ex-DIM) and complemented by multilayered Mie theory. The integrated approach clearly demonstrates the conditions for suppression of the plasmons starting at temperatures well below the melting point. We have found a strong inhomogeneous dependence of the atom mobility in the particle crystal lattice increasing from the center to its surface upon the temperature growth. The plasmon resonance suppression is associated with an increase of the mobility and in the amplitude of phonon vibrations of the lattice atoms accompanied by electron-phonon scattering. This leads to an increase in the relaxation constant impeding the plasmon excitation as the major source of the suppression, while the direct contribution from the increase in the lattice constant and its chaotization at melting is found to be minor. Experimental verification of the suppression of surface plasmon resonance is demonstrated for gold nanoparticles on a quartz substrate heated up to the melting temperature and above. This journal is © The Royal Society of Chemistry., QC 20220930

We study the influence of media on the interaction of ultra-fine plasmonic nanoparticles (≤ 8 nm) with radiation. The important role of the surface layer of the nanoparticles, with properties that differ from the ones in the inner part, is established. Using an atomistic representation of the nanoparticle material and its interaction with light, we find a highly inhomogeneous distribution of the electric field inside and around the particles. It is predicted that with an increase in the refractive index of the ambient medium, the extension of the surface layer of atoms increases, something that also is accompanied by an enhanced red shift of the plasmon resonance band compared to large particles in which the influence of this layer and its relative volume is reduced. It is shown that the physical origin for the formation of a surface layer of atoms near the nanoparticle boundary is related to the anisotropy of the local environment of atoms in this layer which changes the conditions for the interaction of neighboring atoms with each other and with the incident radiation. It is shown that a growth of the refractive index of the ambient medium results in an increase in the local field in the dielectric cavity in which a plasmonic nanoparticle is embedded and which is accompanied by a growth of the amplitude of the plasmon resonance. We predict that in the ultra-fine regime the refractive index sensitivity shows a decreasing trend with respect to size which is opposite to that for larger particles. With the applied atomistic model this work demonstrates close relations between field distributions and properties of ultra-fine nanoparticles., QC 20230607

The interaction of non-monochromatic radiation with arrays comprising plasmonic and dielectric nanoparticles has been studied using the finite-difference time-domain electrodynamics method. It is shown that LiNbO3, TiO2, GaAs, Si, and Ge all-dielectric nanoparticle arrays can provide a complete selective reflection of an incident plane wave within a narrow spectral line of collective lattice resonance with a Q-factor of 103 or larger at various spectral ranges, while plasmonic refractory TiN and chemically stable Au nanoparticle arrays provide high-Q resonances with moderate reflectivity. Arrays with fixed dimensional parameters make it possible to fine-tune the position of a selected resonant spectral line by tilting the array relative to the direction of the incident radiation. These effects provide grounds for engineering novel selective tunable optical high-Q filters in a wide range of wavelengths, from visible to middle-IR., QC 20200303

We propose to utilize titanium nitride (TiN) as an alternative material for linear periodic chains (LPCs) of nanoparticles (NPs) which support surface plasmon polariton (SPP) propagation. Dispersion and transmission properties of LPCs have been examined within the framework of the dipole approximation for NPs with various shapes: spheres, prolate and oblate spheroids. It is shown that LPCs of TiN NPs support high-Q eigenmodes for an SPP attenuation that is comparable with LPCs from conventional plasmonic materials such as Au or Ag, with the advantage that the refractory properties and cheap fabrication of TiN nanostructures are more preferable in practical implementations compared to Au and Ag. We show that the SPP decay in TiN LPCs remains almost the same even at extremely high temperatures which is impossible to reach with conventional plasmonic materials. Finally, we show that the bandwidth of TiN LPCs from non-spherical particles can be tuned from the visible to the telecommunication wavelength range by switching the SPP polarization, which is an attractive feature for integrating these structures into modern photonic devices., QC 20180601

QC 20170509

Molecular aggregates are well known for their customizable optical properties. Vibronic coupling in monomers forming such aggregates offers rich opportunities for property tuning. We study generic molecular aggregate models of growing complexity (from a dimer up to a decamer) and report how vibronic coupling affects aggregate fluorescence intensity. The total aggregate fluorescence intensity is a measure sensitive to both vibronic coupling and Coulomb coupling between monomer transition densities. Using an exact diagonalization approach in the two-particle basis set, we show how the interplay between Coulomb and vibronic coupling affects aggregate fluorescence. Moreover, for H-aggregates we predict a periodic variation of the fluorescence intensity with aggregate size and show that vibronic interaction decreases the effect., QC 20171215

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 particle's 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., QC 20170510

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., Funding text: This work was performed within the State contract of the RF Ministry of Education and Science for Siberian Federal University for scientific research in 2017-2019 and SB RAS Program No II.2P (0358-2015-0010). The calculations were performed using the MVS-1000 M cluster at the Institute of Computational Modeling, Federal Research Center KSC SB RAS.QC 20170530

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., QC 20161219

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.

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.