Measurement and control of optical nonlinearities in dispersive dielectric multilayers.

Dispersive dielectric multilayer mirrors, high-dispersion chirped mirrors in particular, are widely used in modern ultrafast optics to manipulate spectral chirps of ultrashort laser pulses. Dispersive mirrors are routinely designed for dispersion compensation in ultrafast lasers and are assumed to be linear optical components. In this work, we report the experimental characterization of an unexpectedly strong nonlinear response in these chirped mirrors. At modest peak intensities <2 TW/cm2-well below the known laser-induced damage threshold of these dielectric structures-we observed a strong reflectivity decrease, local heating, transient spectral modifications, and time-dependent absorption of the incident pulse. Through computational analysis, we found that the incident laser field can be enhanced by an order of magnitude in the dielectric layers of the structure. The field enhancement leads to a wavelength-dependent nonlinear absorption, that shows no signs of cumulative damage before catastrophic failure. The nonlinear absorption is not a simply two-photon process but instead is likely mediated by defects that facilitate two-photon absorption. To mitigate this issue, we designed and fabricated a dispersive multilayer design that strategically suppresses the field enhancement in the high-index layers, shifting the high-field regions to the larger-bandgap, low-index layers. This strategy significantly increases the maximum peak intensity that the mirror can sustain. However, our finding of an onset of nonlinear absorption even at 'modest' fluence and peak intensity has significant implications for numerous past published experimental works employing dispersive mirrors. Additionally, our results will guide future ultrafast experimental work and ultrafast laser design.

Fluorescent Ag nanoclusters prepared in aqueous poly(acrylic acid-co-maleic acid) solutions: a spectroscopic study of their excited state dynamics, size and local environment.

Stable, fluorescent Ag nanoclusters were prepared in aqueous solutions of Na(+) salt of the carboxylate-rich polymer poly(acrylic acid-co-maleic acid) under brief spells of UV irradiation. The nanoclusters were nearly spherical, with diameters within 1.90 ± 0.50 nm, but displayed a prominent red edge excitation shift (REES) of fluorescence upon exciting within the visible absorption band, indicating heterogeneity of energy level distributions. Spectroscopic studies revealed that irrespective of whether the nanoclusters are excited in their UV or visible absorption bands, their fluorescence always ensues from the same manifold of emissive states, with a broad range of fluorescence lifetimes from ∼150 fs to 1 ns.

Photoisomerization and reorientational dynamics of DTDCI in AOT/alkane reverse micelles containing non-aqueous polar liquids.

Molecular mobility of the symmetric carbocyanine fluorophore DTDCI was studied in AOT/alkane reverse micelles containing non-aqueous polar liquids DMF, formamide, ethylene glycol and glycerol by monitoring both the torsional photoisomerization and rotational reorientation, both of which were sensitive to microviscosity of the local environment. The DTDCI fluorophore resides completely within the AOT-polar liquid reverse micelle nano-droplets, where its dynamics were found to be significantly retarded irrespective of the polar liquid taken, due to a combination of electrostatic and hydrophobic forces that induce the guest DTDC(+) cation to attach to the AOT molecules of the host droplet. The addition of strong hydrogen-bond donating polar liquids like formamide, ethylene glycol and glycerol causes a systematic enlargement of the droplets. Rotational dynamics of the fluorophore inside the nano-droplets was characterized by a diffusion coefficient comparable to that in highly viscous solvents like ethylene glycol.

Local viscosity and solvent relaxation experienced by rod-like fluorophores in AOT/4-chlorophenol/m-xylene organogels.

Organogels prepared from AOT/4-chlorophenol/m-xylene are immobile in the macroscopic sense, with a well-characterized internal structure. However, the molecular level dynamics inside the gels is not too clear, although a very slow structural relaxation has been reported previously. Using a set of rod-like fluorophores, we find that the rotational mobility of a small guest molecule inside the gel can be extremely fast, indicating presence of sufficiently low-microviscosity domains. These domains consist of m-xylene solvent molecules trapped in the interstices of fiber bundles comprising columnar stacks of 4-chlorophenol surrounded by AOT molecules. However, interstitial trapping of m-xylene does retard its own dynamics, which explains the slow solvent relaxation inside the gels. Hence, the state of m-xylene in the organogel may be characterized as "bound", in contrast to the "free" state in neat m-xylene.