Conformable Nanowire-in-Nanofiber Hybrids for Low-Threshold Optical Gain in the Ultraviolet

The miniaturization of diagnostic devices that exploit optical detection schemes requires the design of light sources combining small size, high performance for effective excitation of chromophores, and mechanical flexibility for easy coupling to components with complex and nonplanar shapes. Here, ZnO nanowire-in-fiber hybrids with internal architectural order are introduced, exhibiting a combination of polarized stimulated emission, low propagation losses of light modes, and structural flexibility. Ultrafast transient absorption experiments on the electrospun material show optical gain which gives rise to amplified spontaneous emission with a threshold lower than the value found in films. These systems are highly flexible and can conveniently conform to curved surfaces, which makes them appealing active elements for various device platforms, such as bendable lasers, optical networks, and sensors, as well as for application in bioimaging, photo-cross-linking, and optogenetics

Controlled Multibeam Supercontinuum Generation With a Spatial Light Modulator

We report on deterministic femtosecond multifilamentation in fused silica by encoding a diffractive microlens array into a spatial light modulator. The efficiency and focal length of each microlens are modified through the addressing voltage. This allows for a precise control on the energy coupled to the filaments thus obtaining a homogenized supercontinuum pattern from an inhomogeneous irradiance input distribution. Slight changes in the focal length of the microlenses allow for independent tailoring of the supercontinuum spectra

Dynamic Control of Interference Effects Between Optical Filaments through Programmable Optical Phase Modulation

Light beams shaped by programmable megapixel spatial light modulators (SLMs) are key to broadening the applications of photonics. In this paper, we consider the application of a SLM for the generation of two mutually coherent white-light continuum optical sources by filamentation of infrared femtosecond pulses in bulk. We demonstrate that the inhomogeneity of the input beam and the longitudinal separation of the generated filaments are crucial parameters that break down the mutual coherence across neighboring filaments. We show that local control over the optical phase enables us to gain fine control over filament interference effects.This work was supported by Generalitat Valenciana through the programme (PROMETEO\2012\021), Spanish Ministry of Science under Grant FIS2013-40666-P) and University Jaume I through the project P1 1B2013-53

Diffractive optics for spectral control of the supercontinuum generated in sapphire with femtosecond pulses

We propose the use of kinoform diffractive lenses to focus near infrared femtosecond pulses in sapphire crystals for supercontinuum generation. It is shown that a strongly peaked structure appears in the blue region of the supercontinuum spectra. The central wavelength of this peak can be easily controlled by simply changing the lens-crystal distance. Moreover, when compared with the supercontinuum generated with a refractive lens in analogous conditions, the spectral extension of the so-generated continuum is larger. Our results were corroborated for sapphire plates with different thicknesses as well as in other transparent dielectrics such as fused silica.Support from Spanish Ministerio de Ciencia e Innovación (MICINN) through the Consolider Program SAUUL CSD2007-00013, research projects FIS2009-09522 and FIS2010-15746, and from Junta de Castilla y León through the Program for Groups of Excellence (GR27). CR and RBV acknowledge MICINN for support through grants BES-2007-17415 and AP2007-00202, respectively. GMV and OMY gratefully acknowledge partial financial support from Convenio UJI-Bancaixa under the project P1-1B2010-26.We also acknowledge support from the Centro de Láseres Pulsados (CLPU) (Salamanca, Spain

Coherent vibrational modes promote the ultrafast internal conversion and intersystem crossing in thiobases

Thionated nucleobases are obtained by replacing oxygen with sulphur atoms in the canonical nucleobases. They absorb light efficiently in the near-ultraviolet, populating singlet states which undergo intersystem crossing to the triplet manifold on an ultrashort time scale with a high quantum yield. Nonetheless there are still important open questions about the primary mechanisms responsible for this ultrafast transition. Here we track both the electronic and the vibrational ultrafast excited-state dynamics towards the triplet state for solvated 4-thiothymidine (4TT) and 4-thiouracil (4TU) with sub-30 fs broadband transient absorption spectroscopy in the ultraviolet. A global and target analysis allows us to simultaneously resolve the contributions of the different electronically and vibrationally excited states to the whole data set. Our experimental results, combined with state-of-the-art quantum mechanics/molecular mechanics simulations and Damped Oscillation Associated Spectra (DOAS) and target analysis, support that the relaxation to the triplet state is mediated by conical intersections promoted by vibrational coherences through the population of an intermediate singlet state. In addition, the analysis of the coherent vibrational dynamics reveals that, despite sharing the same relaxation mechanism and similar chemical structures, 4TT and 4TU exhibit rather different geometrical deformations, characterized by the conservation of planarity in 4TU and its partial rupture in 4TT

A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub-20 fs broadband transient absorption spectroscopy in the near-UV are combined with CASPT2/MM decay path calculations to unravel the excited-state decay channels of water solvated 2-thio and 2,4-dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4-dithiouracil decay pathways is shown to be strongly correlated either to those of 2- or 4-thiouracil, depending on the sulfur atom on which the electronic transition localizes

Environment-Driven Coherent Population Transfer Governs the Ultrafast Photophysics of Tryptophan

By combining UV transient absorption spectroscopy with sub-30-fs temporal resolution and CASPT2/MM calculations, we present a complete description of the primary photo-induced processes in solvated tryptophan. Our results shed new light on the role of the solvent in the relaxation dynamics of tryptophan. We unveil two consecutive coherent population transfer events involving the lowest two singlet excited states: a sub-50-fs non-adiabatic La-->Lb transfer through a conical intersection and a subsequent 220 fs reverse Lb-->La transfer due to solvent assisted adiabatic stabilization of the La state. Vibrational fingerprints in the transient absorption spectra provide compelling evidence of a vibronic coherence established between the two excited states from the earliest times after photoexcitation and lasting until the back-transfer to La is complete. The demonstration of response to the environment as a driver of coherent population dynamics among the excited states of tryptophan closes the long debate on its solvent-assisted relaxation mechanisms and extends its application as a local probe of protein dynamics to the ultrafast timescales

Electron and ion spectroscopy of azobenzene in the valence and core shells

Azobenzene is a prototype and a building block of a class of molecules of extreme technological interest as molecular photo-switches. We present a joint experimental and theoretical study of its response to irradiation with light across the UV to x-ray spectrum. The study of valence and inner shell photo-ionization and excitation processes combined with measurement of valence photoelectron-photoion coincidence and mass spectra across the core thresholds provides a detailed insight into the site- and state-selected photo-induced processes. Photo-ionization and excitation measurements are interpreted via the multi-configurational restricted active space self-consistent field method corrected by second order perturbation theory. Using static modeling, we demonstrate that the carbon and nitrogen K edges of azobenzene are suitable candidates for exploring its photoinduced dynamics thanks to the transient signals appearing in background-free regions of the NEXAFS and XPS

Ultrafast-nonlinear ultraviolet pulse modulation in an AlInGaN polariton waveguide operating up to room temperature

Ultrafast nonlinear photonics enables a host of applications in advanced on-chip spectroscopy and information processing. These rely on a strong intensity dependent (nonlinear) refractive index capable of modulating optical pulses on sub-picosecond timescales and on length scales suitable for integrated photonics. Currently there is no platform that can provide this for the UV spectral range where broadband spectra generated by nonlinear modulation can pave the way to new on-chip ultrafast (bio-) chemical spectroscopy devices. We introduce an AlInGaN waveguide supporting highly nonlinear UV hybrid light-matter states (exciton-polaritons) up to room temperature. We experimentally demonstrate ultrafast nonlinear spectral broadening of UV pulses in a compact 100 micrometer long device and measure a nonlinearity 1000 times that in common UV nonlinear materials and comparable to non-UV polariton devices. Our demonstration, utilising the mature AlInGaN platform, promises to underpin a new generation of integrated UV nonlinear light sources for advanced spectroscopy and measurement