Picosecond-jet spectroscopy and photochemistry. Energy redistribution and its impact on coherence, isomerization, dissociation and solvation

The development of the picosecond-jet technique is presented. The applications of the technique to the studies of coherence (quantum beats), photodissociation, isomerization and partial solvation of molecules in supersonic-jet beams are detailed with emphasis on the role of intramolecular energy redistribution. Experimental evidence for intramolecular threshold effect for rates as a function of excess molecular energy is given and explained using simple theory for the redistribution of energy among certain modes. Comparison with R.R.K.M. calculation is also made to assess the nature of the statistical behaviour of the energy redistribution

Femtosecond transition-state dynamics

This article presents the progress made in probing femtosecond transition–state dynamics of elementary reactions. Experiments demonstrating the dynamics in systems characterized by a transition region and by a saddle-point transition state are reported, and comparison with theory is made

Femtochemistry: the role of alignment and orientation

Some aspects of alignment and orientation have been considered for femtochemistry experiments. Elementary theoretical descriptions of the time evolution of alignment and angular momenta have been discussed and related to the radial and angular parts of the potential-energy surface. Applications to ICN unimolecular dissociation, H + CO2oriented bimolecular reaction, and crossings between different potential-energy curves in alkali-metal halide reactions (M + X) are give. Emphasis is on the femtosecond dynamics of the transition-state region and the clocking of fragment separation in real time

New Light on Molecular and Materials Complexity: 4D Electron Imaging

In this Perspective, 4D electron imaging is highlighted, after introducing some concepts, with an overview of selected applications that span chemical reactions, molecular interfaces, phase transitions, and nano(micro)mechanical systems. With the added dimension of time in microscopy, diffraction, and electron-energy-loss spectroscopy, the focus is on direct visualization of structural dynamics with atomic and nanoscale resolution in the four dimensions of space and time. This contribution provides an expose of emerging developments and an outlook on future applications in materials and biological sciences

DC fault isolation study of bidirectional dual active bridge DC/DC converter for DC transmission grid application

Fast isolation and detection of DC faults is currently a limiting factor in high power DC transmission grid development. Recent research has shown that the role of DC/DC converters is becoming increasingly important in solving various DC grid challenges such as voltage stepping, galvanic isolation and power regulation. This paper focuses on an additional important feature of bidirectional dual active bridge (DAB) DC-DC converters which make it attractive for future DC grids; it's inherent fault isolation capability which does not need control intervention to limit fault current in case of the most severe DC faults. Detailed analytical, simulation and experimental study are performed by subjecting the converter to DC short circuit faults at its DC voltage terminals. The results obtained have shown significant advantage of DAB where fault current is less than rated current during the fault duration. Thus no control action is necessary from the non-faulted bridge to limit fault current and no external DC circuit breakers are required. This advantage makes DAB converter feasible for DC grid integration

Analysis of AC link topologies in non-isolated DC/DC triple active bridge converter for current stress minimization

This paper presents analysis of the non-isolated DC/DC triple active bridge (TAB) converter under various purely inductor-based AC link topologies. The objective of the analysis is to find the topology that incorporates the least value of the AC link inductors which leads to reduced converter footprint in addition to minimum internal current stresses. Modelling of the TAB under each of the different topologies is presented in per unit expressions of power transfer and reactive power assuming fundamental harmonic analysis. The power expressions are used to calculate the inductor values necessary to achieve same rated power transfer of Dual Active Bridge (DAB) converter for the sake of standardizing comparison. On this basis, the topology requiring the least value of interface inductors, hence lowest footprint, is identified. Furthermore, based on phase shift control, particle swarm optimization (PSO) is used to calculate optimal phase shift ratios in each of the proposed topologies to minimize reactive power loss (hence current stress). The topology with minimum stresses is therefore identified and the results are substantiated using a Matlab-Simulink model to verify the theoretical analysis

4D Scanning Transmission Ultrafast Electron Microscopy: Single-Particle Imaging and Spectroscopy

We report the development of 4D scanning transmission ultrafast electron microscopy (ST-UEM). The method was demonstrated in the imaging of silver nanowires and gold nanoparticles. For the wire, the mechanical motion and shape morphological dynamics were imaged, and from the images we obtained the resonance frequency and the dephasing time of the motion. Moreover, we demonstrate here the simultaneous acquisition of dark-field images and electron energy loss spectra from a single gold nanoparticle, which is not possible with conventional methods. The local probing capabilities of ST-UEM open new avenues for probing dynamic processes, from single isolated to embedded nanostructures, without being affected by the heterogeneous processes of ensemble-averaged dynamics. Such methodology promises to have wide-ranging applications in materials science and in single-particle biological imaging

Femtosecond dynamics of flavoproteins: Charge separation and recombination in riboflavine (vitamin B_2)-binding protein and in glucose oxidase enzyme

Flavoproteins can function as hydrophobic sites for vitamin B_2 (riboflavin) or, in other structures, with cofactors for catalytic reactions such as glucose oxidation. In this contribution, we report direct observation of charge separation and recombination in two flavoproteins: riboflavin-binding protein and glucose oxidase. With femtosecond resolution, we observed the ultrafast electron transfer from tryptophan(s) to riboflavin in the riboflavin-binding protein, with two reaction times: approx 100 fs (86% component) and 700 fs (14%). The charge recombination was observed to take place in 8 ps, as probed by the decay of the charge-separated state and the recovery of the ground state. The time scale for charge separation and recombination indicates the local structural tightness for the dynamics to occur that fast and with efficiency of more than 99%. In contrast, in glucose oxidase, electron transfer between flavin-adenine-dinucleotide and tryptophan(s)/tyrosine(s) takes much longer times, 1.8 ps (75%) and 10 ps (25%); the corresponding charge recombination occurs on two time scales, 30 ps and nanoseconds, and the efficiency is still more than 97%. The contrast in time scales for the two structurally different proteins (of the same family) correlates with the distinction in function: hydrophobic recognition of the vitamin in the former requires a tightly bound structure (ultrafast dynamics), and oxidation-reduction reactions in the latter prefer the formation of a charge-separated state that lives long enough for chemistry to occur efficiently. Finally, we also studied the influence on the dynamics of protein conformations at different ionic strengths and denaturant concentrations and observed the sharp collapse of the hydrophobic cleft and, in contrast, the gradual change of glucose oxidase