Nonlinear and thermo-optical characterisation of bare imidazolium ionic liquids.

Nonlinear optical (NLO) and thermo-optical properties of two pure ionic liquids, BMIOMe.NTf2 and BMIOMe.N(CN)2, were examined in this study. This was the first nonlinear refractive index determination of a pristine ionic liquid by a standard self-refraction experiment. The NLO characterisations were performed using Z-scan and EZ-scan techniques in the thermally managed approach, with a mode-locked femtosecond laser source. Thermal properties were analysed concomitantly, and the thermo-optical coefficient, thermal characteristic time, and lens strength were characterised. These results define the parameters to be adopted in the method of nanoparticles formation by laser ablation in an ionic liquid solution and indicate that BMIOMe.NTf2 is a prominent material to be engineered for photonics applications.

Super rogue wave generation in the linear regime.

Extreme or rogue waves are large and unexpected waves appearing with higher probability than predicted by Gaussian statistics. Although their formation is explained by both linear and nonlinear wave propagation, nonlinearity has been considered a necessary ingredient to generate super rogue waves, i.e., an enhanced wave amplification, where the wave amplitudes exceed by far those of ordinary rogue waves. Here we show, experimentally and theoretically, that optical super rogue waves emerge in the simple case of linear light diffraction in one transverse dimension. The underlying physics is a long-range correlation on the random initial phases of the light waves. When subgroups of random phases appear recurrently along the spatial phase distribution, a more ordered phase structure greatly increases the probability of constructive interference to generate super rogue events (non-Gaussian statistics with superlong tails). Our results consist in a significant advance in the understanding of extreme waves formation by linear superposition of random waves, with applications in a large variety of wave systems.

Splitting an optical vortex beam to study photonic orbit-orbit interactions.

We numerically and experimentally evidence photonic orbit-orbit interactions in freely propagating asymmetrical beams carrying orbital angular momentum. A Fresnel biprism is used to carry out the wavefront division of an optical vortex beam, generating two complementary asymmetrical beams. The optical orbital Hall effect is presented in the form of angular deviations from the beam's geometrical expectation. We also observe the rotation of the field transverse profile near the nominal propagation axis upon propagation, which direction depends on orbital momentum currents.

Synthesis and Characterisation of Fluorescent Carbon Nanodots Produced in Ionic Liquids by Laser Ablation.

Carbon nanodots (C-dots) with an average size of 1.5 and 3.0 nm were produced by laser ablation in different imidazolium ionic liquids (ILs), namely, 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI.BF4 ), 1-n-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMI.NTf2 ) and 1-n-octyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (OMI.NTf2 ). The mean size of the nanoparticles is influenced by the imidazolium alkyl side chain but not by the nature of the anion. However, by varying the anion (BF4 vs. NTf2 ) it was possible to detect a significant modification of the fluorescence properties. The C-dots are much probably stabilised by an electrostatic layer of the IL and this interaction has played an important role with regard to the formation, stabilisation and photoluminescence properties of the nanodots. A tuneable broadband fluorescence emission from the colloidal suspension was observed under ultraviolet/visible excitation with fluorescence lifetimes fitted by a multi-exponential decay with average values around 7 ns.

Light with Tunable Non-Markovian Phase Imprint.

We introduce a simple and flexible method to generate spatially non-Markovian light with tunable coherence properties in one and two dimensions. The unusual behavior of this light is demonstrated experimentally by probing the far field and by recording its diffraction pattern after a double slit: In both cases we observe, instead of a central intensity maximum, a line- or cross-shaped dark region, whose width and profile depend on the non-Markovian coherence properties. Because these properties can be controlled and easily reproduced in experiment, the presented approach lends itself to serving as a test bed to study and gain a deeper understanding of non-Markovian processes.

Mapping impurity of single-walled carbon nanotubes in bulk samples with multiplex coherent anti-stokes Raman microscopy.

Mapping of defects in bulk samples of single-walled carbon nanotubes (SWNT) is performed via multiplex coherent anti-Stokes Raman microscopy. The D and G vibrational bands are acquired simultaneously, and their relative amplitude is used as a criterion to quantify the local purity in spin-coated SWNT samples. We observe that defects induced by oxidation are related to the spatial dispersion of nanotubes in a solid distribution.

Simple modeling of plasmon resonances in Ag/SiO2 nanocomposite monolayers.

Normal incidence transmittance and reflectance spectra of sputtered nanocomposite monolayer films of Ag in SiO2, buried and unburied, showed significant redshifted plasmon resonances from 410 to 455 nm, which could be well interpreted with a simple model that starts from the Maxwell Garnett theory and the Kreibig extension of the Drude-Lorentz equation, but with a further extension related to the dipolar interaction between the metal particles distributed on a surface.

Structural control of gold nanoparticles self-assemblies by layer-by-layer process.

This work presents a novel way to introduce gold nanoparticles (Au NPs) in a multilayer polymer produced by the layer-by-layer (LbL) assembling technique. The technique chosen shows that, depending on the pH used, different morphological structures can be obtained from monolayer or bilayer Au NPs. The MEIS and RBS techniques allowed for the modelling of the interface polymer-NPs, as well as the understanding of the interaction of LbL system, when adjusting the pH in weak polyelectrolytes. The process reveals that the optical properties of multilayer systems could be fine-tuned by controlling the addition of metallic nanoparticles, which could also modify specific polarization responses.

Synthesis of gold nanoparticles by laser ablation of an Au foil inside and outside ionic liquids.

Stable gold nanoparticles (AuNPs) were prepared by simple laser ablation of an Au foil placed inside or outside four ionic liquids (ILs), without the addition of any external chemical reagent. Irregular spherical AuNPs with a diameter range of 5 to 20 nm were produced after laser ablation of an Au foil located inside or outside the ILs 1-n-butyl-3-methylimidazolium tetrafluoroborate (BMI·BF4), 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI·PF6) and 1-(3-cyanopropyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ((BCN)MI·NTf2). Additionally, whereas laser ablation inside the IL 1-n-butyl-3-methylimidazolium dicyanamide BMI·N(CN)2 produced flower-like shaped nanoparticles of about 50 nm in size, ablation outside this IL presented similar results to the others ILs studied, as determined by TEM and UV-Vis. The size and shape of the prepared NPs were related to where NP nucleation and growth occurred, i.e., at the IL surface or within the IL. Indeed, the chemical composition of the IL/air interface and surface ion orientation played important roles in the stabilization of the AuNPs formed by laser ablation outside the ILs.

Molecular dynamics investigation with the time resolved optical Kerr effect on the CS2-C6H6 mixtures.

An investigation of the molecular dynamics in pure liquids and in mixtures through the technique of time resolved optical Kerr effect is performed. The samples studied were the mixtures of carbon disulfide (CS(2)) with benzene (C(6)H(6)). The molecular dynamics of the pure liquids is briefly discussed while the main results are obtained for the mixtures. A slow dynamics component is observed for the optical heterodyne detected optical Kerr effect transient decaying exponentially with time constants on picosecond time scale. The fast subpicosend time relaxations are analyzed in terms of the nondiffusive component of the spectral response that is associated with the molecular dynamics. The modifications of the spectrum are quantified, and the explanation of the observed changes is given in terms of the structural interaction configurations that produced changes in the intermolecular potential within which the molecules execute librational motions.

Pump-probe and pump-deplete-probe spectroscopies on carotenoids with N=9-15 conjugated bonds.

A series of all-trans-carotenoids with N=9, 13, and 15 conjugated bonds has been studied by pump-probe and pump-deplete-probe spectroscopies to obtain a systematic analysis of the energy flow between the different electronic states. The ultrafast dynamics in the carotenoids are initialized by excitation to the S2 state and subsequently manipulated by an additional depletion pulse in the near-IR spectral range. The changes in the dynamics after depletion of the excited state population allowed differentiation of the excited state absorption into two components, a major one corresponding to the well known S1 state and the small contribution on the red wing of the S0-S2 absorption band originating from the hot ground state. We found no evidence for an additional electronically excited state, usually called S*. Instead, a deactivation mechanism that includes the hot ground state supports the observed results nicely in the framework of a simple three state model (S2, S1, and S0).

Time-resolved optical Kerr-effect investigation on CS2/polystyrene mixtures.

The relaxation dynamics of carbon disulfide are investigated in mixtures with polystyrene (PS) using the time-resolved optical heterodyne-detected optical Kerr effect (OHD-OKE). The data are analyzed using both the model-dependent approach, which assumes four distinct temporal responses, and the model-independent Fourier transform approach, which generates a spectral response that can be compared with results obtained by depolarized Rayleigh scattering. A slow dynamics is observed for the OHD-OKE transient decaying exponentially with a time constant that varies from 1.68 ps for neat CS2 to 3.76 ps for the most concentrated CS2PS mixture. The increase of this time constant accompanies an increase in the viscosity of the mixture, so we can associate this component with the diffusive reorientation process of the induced polarizability anisotropy of the carbon disulfide in the mixture. The short-time nuclear response is characterized in the frequency domain by a broad band that peaks around 30 cm(-1) for neat carbon disulfide, and is associated with a complex relaxation pattern. The vibrational distribution shifts to higher frequencies when the PS concentration is increased in the mixture. This result is discussed in terms of an increase in the interaction strength between the PS phenyl rings and the carbon disulfide molecules.

Characterization of ultrashort pulses by a modified grating-eliminated no-nonsense observation of ultrafast incident laser light E fields (GRENOUILLE) method.

The measurement and characterization of ultrashort laser pulses remains an arduous task. The most commonly used pulse-measurement method is known as frequency-resolved optical gating (FROG), and another version with great experimental simplification and low-priced setup is known as grating-eliminated no-nonsense observation of ultrafast incident laser light E fields (GRENOUILLE). Nevertheless, there is interest in elaborating other, more accessible or simpler and cheaper, setups with equal or better assets. We explored modification of the GRENOUILLE method in which we replaced the original Fresnel biprism with a beam splitter and two mirrors and used a cheap webcam to measure the pulse traces. We have evaluated our system, and we propose a method to correct border effects caused by the beam intensity's profile based on the characterization of three pulse classes: Fourier-transform limited, double, and chirped. We compare the recovered electric field with further spectral and second-order correlation data of the corresponding pulses.

Laser-induced fragmentation of transition metal nanoparticles in ionic liquids.

Stable Pd(0) and Rh(0) nanoparticles with small and narrow size distribution can be prepared from relative large and agglomerated transition-metal particles dispersed in 1-n-butyl-3methylimidazolium hexafluorophosphate ionic liquid by simple laser irradiation. The laser irradiation is a complementary method for the generation of stable metal colloids in ionic liquids and also for the regeneration of small-size nanoparticles that may result from their agglomeration after different applications.