Ultrafast transient absorption spectroscopy: principles and applications

The study of photophysical and photochemical processes crosses the interest of many fields of research in physics, chemistry and biology. In particular, the photophysical and photochemical reactions, after light absorption by a photosynthetic pigment-protein complex, are among the fastest events in biology, taking place on timescales ranging from tens of femtoseconds to a few nanoseconds. Among the experimental approaches developed for this purpose, the advent of ultrafast transient absorption spectroscopy has become a powerful and widely used technique.[1,2] Focusing on the process of photosynthesis, it relies upon the efficient absorption and conversion of the radiant energy from the Sun. Chlorophylls and carotenoids are the main players in the process. Photosynthetic pigments are typically arranged in a highly organized fashion to constitute antennas and reaction centers, supramolecular devices where light harvesting and charge separation take place. The very early steps in the photosynthetic process take place after the absorption of a photon by an antenna system, which harvests light and eventually delivers it to the reaction center. In order to compete with internal conversion, intersystem crossing, and fluorescence, which inevitably lead to energy loss, the energy and electron transfer processes that fix the excited-state energy in photosynthesis must be extremely fast. In order to investigate these events, ultrafast techniques down to a sub-100 fs resolution must be used. In this way, energy migration within the system as well as the formation of new chemical species such as charge-separated states can be tracked in real time. This can be achieved by making use of ultrafast transient absorption spectroscopy. The basic principles of this notable technique, instrumentation, and some recent applications to photosynthetic systems[3] will be described. Acknowledgements M. Moreno Oliva thanks the MINECO for a “Juan de la Cierva-Incorporación” research contract. References [1] U. Megerle, I. Pugliesi, C. Schriever, C.F. Sailer and E. Riedle, Appl. Phys. B, 96, 215 – 231 (2009). [2] R. Berera, R. van Grondelle and J.T.M. Kennis, Photosynth. Res., 101, 105 – 118 (2009). [3] T. Nikkonen, M. Moreno Oliva, A. Kahnt, M. Muuronen, J. Helaja and D.M. Guldi, Chem. Eur. J., 21, 590 – 600 (2015).

Channel plasmon-polariton modes in V grooves filled with dielectric

We investigated the effect of dielectric filling in a V groove on the propagation parameters of channel plasmon-polariton (CPP) modes. In particular, existence conditions and critical groove angles, mode localization, field structure, dispersion, and propagation distances of CPP modes are analyzed as functions of dielectric permittivity inside the groove. It is demonstrated that increasing dielectric permittivity in the groove results in a rapid increase of mode localization near the tip of the groove and increase of both the critical angles that determine a range of groove angles for which CPP modes can exist. Detailed analysis of the field structure has demonstrated that the maximum of the field in a CPP mode is typically reached at a small distance from the tip of the groove. The effect of rounded tip is also investigated.

Identification of a cryptic Prokaryotic promoter within the cDNA encoding the 5′ End of Dengue Virus RNA Genome

Infectious cDNA clones of RNA viruses are important research tools, but flavivirus cDNA clones have proven difficult to assemble and propagate in bacteria. This has been attributed to genetic instability and/or host cell toxicity, however the mechanism leading to these difficulties has not been fully elucidated. Here we identify and characterize an efficient cryptic bacterial promoter in the cDNA encoding the dengue virus (DENV) 5′ UTR. Following cryptic transcription in E. coli, protein expression initiated at a conserved in-frame AUG that is downstream from the authentic DENV initiation codon, yielding a DENV polyprotein fragment that was truncated at the N-terminus. A more complete understanding of constitutive viral protein expression in E. coli might help explain the cloning and propagation difficulties generally observed with flavivirus cDNA.

A compact interferometric sensor design using three waveguide coupling

The use of metal stripes for the guiding of plasmons is a well established technique for the infrared regime and has resulted in the development of a myriad of passive optical components and sensing devices. However, the plasmons suffer from large losses around sharp bends, making the compact design of nanoscale sensors and circuits problematic. A compact alternative would be to use evanescent coupling between two sufficiently close stripes, and thus we propose a compact interferometer design using evanescent coupling. The sensitivity of the design is compared with that achieved using a hand-held sensor based on the Kretschmann style surface plasmon resonance technique. Modeling of the new interferometric sensor is performed for various structural parameters using finite-difference time-domain and COMSOL Multiphysics. The physical mechanisms behind the coupling and propagation of plasmons in this structure are explained in terms of the allowed modes in each section of the device.

Atomistic exploration of deformation properties of copper nanowires with pre-existing defects

Based on the embedded atom method (EAM) and molecular dynamics (MD) method, in this paper, the tensile deformation properties of Cu nanowires (NWs) with different pre-existing defects, including single surface defects, surface bi-defects and single internal defects, are systematically studied. In-depth deformation mechanisms of NWs with pre-existing defects are also explored. It is found that Young's modulus is insensitive to different pre-existing defects, but yield strength shows an obvious decrease. Defects are observed influencing greatly on NWs' tensile deformation mechanisms, and playing a role of dislocation sources. Besides of the traditional deformation process dominated by the nucleation and propagation of partial dislocations, the generations of twins, grain boundaries, fivefold deformation twins, hexagonal close-packed (HCP) structure and phase transformation from face-centred cubic (FCC) structure to HCP structure have been triggered by pre-existing defects. It is found that surface defect intends to induce larger influence to yield strength than internal defect. Most importantly, the defect that lies on slip planes exerts larger influence than other defects. As expected, it is also found that the more or longer of the defect, the bigger influence will be induced.

Numerical Characterization of Nanowires

In this chapter, we will present a contemporary review of the hitherto numerical characterization of nanowires (NWs). The bulk of the research reported in the literatures concern metallic NWs including Al, Cu, Au, Ag, Ni, and their alloys NWs. Research has also been reported for the investigation of some nonmetallic NWs, such as ZnO, GaN, SiC, SiO2. A plenty of researches have been conducted regarding the numerical investigation of NWs. Issues analyzed include structural changes under different loading situations, the formation and propagation of dislocations, and the effect of the magnitude of applied loading on deformation mechanics. Efforts have also been made to correlate simulation results with experimental measurements. However, direct comparisons are difficult since most simulations are carried out under conditions of extremely high strain/loading rates and small simulation samples due to computational limitations. Despite of the immense numerical studies of NWs, a significant work still lies ahead in terms of problem formulation, interpretation of results, identification and delineation of deformation mechanisms, and constitutive characterization of behavior. In this chapter, we present an introduction of the commonly adopted experimental and numerical approaches in studies of the deformation of NWs in Section 1. An overview of findings concerning perfect NWs under different loading situations, such as tension, compression, torsion, and bending are presented in Section 2. In Section 3, we will detail some recent results from the authors’ own work with an emphasis on the study of influences from different pre-existing defect on NWs. Some thoughts on future directions of the computational mechanics of NWs together with Conclusions will be given in the last section.

Bending properties of Ag nanowires with pre-existing surface defects

Materials used in the engineering always contain imperfections or defects which significantly affect their performances. Based on the large-scale molecular dynamics simulation and the Euler–Bernoulli beam theory, the influence from different pre-existing surface defects on the bending properties of Ag nanowires (NWs) is studied in this paper. It is found that the nonlinear-elastic deformation, as well as the flexural rigidity of the NW is insensitive to different surface defects for the studied defects in this paper. On the contrary, an evident decrease of the yield strength is observed due to the existence of defects. In-depth inspection of the deformation process reveals that, at the onset of plastic deformation, dislocation embryos initiate from the locations of surface defects, and the plastic deformation is dominated by the nucleation and propagation of partial dislocations under the considered temperature. Particularly, the generation of stair-rod partial dislocations and Lomer–Cottrell lock are normally observed for both perfect and defected NWs. The generation of these structures has thwarted attempts of the NW to an early yielding, which leads to the phenomenon that more defects does not necessarily mean a lower critical force.

Torsional properties of bamboo-like structured Cu nanowires

Recently, researchers reported that nanowires (NWs) are often polycrystalline, which contain grain or twin boundaries that transect the whole NW normal to its axial direction into a bamboo like structure. In this work, large-scale molecular dynamics simulation is employed to investigate the torsional behaviours of bamboo-like structured Cu NWs. The existence of grain boundaries is found to induce a considerably large reduction to the critical angle, and the more of grain boundaries the less reduction appears, whereas, the presence of twin boundaries only results in a relatively smaller reduction to the critical angle. The introduction of grain boundaries reduces the torsional rigidity of the NW, whereas, the twin boundaries exert insignificant influence to the torsional rigidity. NWs with grain boundaries are inclined to produce a local HCP structure during loading, and the plastic deformation is usually evenly distributed along the axial axis of the NW. The plastic deformation of both perfect NW and NWs with twin boundaries is dominated by the nucleation and propagation of parallel intrinsic stacking faults. This study will enrich the current understanding of the mechanical properties of NWs, which will eventually shed lights on their applications.

From short pulses to short breaks : exotic plasma bullets via residual electron control

Plasma plumes with exotically segmented channel structure and plasma bullet propagation are produced in atmospheric plasma jets. This is achieved by tailoring interruptions of a continuous DC power supply over the time scales of lifetimes of residual electrons produced by the preceding discharge phase. These phenomena are explained by studying the plasma dynamics using nanosecond-precision imaging. One of the plumes is produced using 2-10μs interruptions in the 8kV DC voltage and features a still bright channel from which a propagating bullet detaches. A shorter interruption of 900ns produces a plume with the additional long conducting dark channel between the jet nozzle and the bright area. The bullet size, formation dynamics, and propagation speed and distance can be effectively controlled. This may lead to micrometer-and nanosecond-precision delivery of quantized plasma bits, warranted for next-generation health, materials, and device technologies.

Analysis of distributed beamforming in cooperative communications network with phase shifter based smart antenna nodes

This research study investigates the application of phase shifter-based smart antenna system in distributed beamforming. It examines the way to optimise the transmit power by jointly maximising the directivity of the array antennas and the weight vector for distributed beamforming. This research study concludes that maximising directivity can lead to better transmit power minimisation compared to maximising field intensity. This study also concludes that signal to noise power ratio maximisation subject to a power constraint and power minimisation subject to a signal to noise power ratio constraint yield the same results.

Stress-induced martensitic phase transformation in Cu-Zr nanowires

A novel stress-induced martensitic phase transformation in an initial < 100 >/{100} B2-CuZr nanowire is reported for the first time in this letter. Such behavior is observed in a nanowire with cross-sectional dimensions of 19.44 x 19.44 angstrom(2) over a temperature range of 100-400 K and at a strain rate of 1 x 10(9) s(-1) using atomistic simulations. Phase transformation from an initial B2 phase to a BCT (Body-Centered-Tetragonal) phase is observed via nucleation and propagation of {100} twinning plane under high strain rate tensile deformation. (C) 2009 Elsevier B.V. All rights reserved.

Solid-state Thermal Polymerization of Sodium Acrylate

Initiation and propagation processes in thermally initiated solid-state polymerization of sodiumvacrylate have been studied. The kinetics of initiation, followed with the electron spin resonancev technique, leads to an activation energy E of 28.8 kcal/mol, which is attributed to the formation of dimeric radicals. The activation energy of 16 f 1 kcaVmol obtained for the solid-state polymerization of sodium acrylate by chemical analysis and differential scanning calorimetry has been attributed to the propagation process.

Multipath Dissemination in Regular Mesh Topologies

Mesh topologies are important for large-scale peer-to-peer systems that use low-power transceivers. The Quality of Service (QoS) in such systems is known to decrease as the scale increases. We present a scalable approach for dissemination that exploits all the shortest paths between a pair of nodes and improves the QoS. Despite th presence of multiple shortest paths in a system, we show that these paths cannot be exploited by spreading the messages over the paths in a simple round-robin manner; nodes along one of these paths will always handle more messages than the nodes along the other paths. We characterize the set of shortest paths between a pair of nodes in regular mesh topologies and derive rules, using this characterization, to effectively spread the messages over all the available paths. These rules ensure that all the nodes that are at the same distance from the source handle roughly the same number of messages. By modeling the multihop propagation in the mesh topology as a multistage queuing network, we present simulation results from a variety of scenarios that include link failures and propagation irregularities to reflect real-world characteristics. Our method achieves improved QoS in all these scenarios.

Sensing Shape Recovery Using Conductivity Noise in Thin Films of NiTi Shape Memory Alloys

Low frequency fluctuations in the electrical resistivity, or noise, have been used as a sensitive tool to probe into the temperature driven martensite transition in dc magnetron sputtered thin films of nickel titanium shape-memory alloys. Even in the equilibrium or static case, the noise magnitude was more than nine orders of magnitude larger than conventional metallic thin films and had a characteristic dependence on temperature. We observe that the noise while the temperature is being ramped is far larger as compared to the equilibrium noise indicating the sensitivity of electrical resistivity to the nucleation and propagation of domains during the shape recovery. Further, the higher order statistics suggests the existence of long range correlations during the transition. This new characterization is based on the kinetics of disorder in the system and separate from existing techniques and can be integrated to many device applications of shape memory alloys for in-situ shape recovery sensing.

Delay time of a vacuum gap triggered by an exploding wire

The experimental results of delay time of a vacuum gap triggered by an exploding wire plasma have been reported. It consists of explosion delay time and propagation delay time. The explosion delay time has been found to be dependent on the parameters of the exploding wire and the exploding wire circuit and is independent of vacuum gap configuration. The propagation delay time depends on the properties of the exploding wire plasma and vacuum gap parameters such as the number of injection slots, gap spacing, gap polarity, etc. In the absence of prebreakdown current in the vacuum gap, the breakdown can be initiated only after the plasma completely bridges the gap spacing. Under this specific condition, it has been shown that the delay time data can be used to calculate the plasma velocity.