Strain wave pathway to semiconductor-to-metal transition revealed by time-resolved X-ray powder diffraction.

One of the main challenges in ultrafast material science is to trigger phase transitions with short pulses of light. Here we show how strain waves, launched by electronic and structural precursor phenomena, determine a coherent macroscopic transformation pathway for the semiconducting-to-metal transition in bistable Ti3O5 nanocrystals. Employing femtosecond powder X-ray diffraction, we measure the lattice deformation in the phase transition as a function of time. We monitor the early intra-cell distortion around the light absorbing metal dimer and the long range deformations governed by acoustic waves propagating from the laser-exposed Ti3O5 surface. We developed a simplified elastic model demonstrating that picosecond switching in nanocrystals happens concomitantly with the propagating acoustic wavefront, several decades faster than thermal processes governed by heat diffusion.

Increased left inferior fronto-striatal activation during error monitoring after fMRI neurofeedback of right inferior frontal cortex in adolescents with attention deficit hyperactivity disorder.

Attention Deficit/Hyperactivity Disorder (ADHD) is a self-regulation disorder, with impairments in error monitoring associated with underactivation of the related brain network(s). Psychostimulant medication improves ADHD symptoms and can upregulate brain function, but has side effects, with limited evidence for longer-term effects. Real-time functional magnetic resonance neurofeedback (fMRI-NF) has potential longer-term neuroplastic effects. We previously reported the effects of 11 runs of 8.5 min of fMRI-NF of the right inferior frontal cortex (rIFC) in adolescents with ADHD. This resulted in improvement of clinical symptom and enhanced rIFC activation post-pre treatment during response inhibition, when compared to a control group receiving fMRI-NF of the left parahippocampal gyrus (lPHG). In the current study we applied a novel analysis to the existing data by investigating the effects of fMRI-NF of rIFC in 16 adolescents with ADHD compared to fMRI-NF of lPHG in 11 adolescents with ADHD on the neurofunctional correlates of error monitoring during the same fMRI tracking stop task and potential associations with cognitive and clinical measures. We found stronger performance adjustment to errors in the rIFC-NF compared to the control lPHG-NF group. At the brain function level, fMRI-NF of rIFC compared to that of lPHG was associated with increased activation in error monitoring regions of the left IFC, premotor cortex, insula and putamen. The increased activation in left IFC-insular-striatal error monitoring regions in the rIFC-NF relative to the lPHG-NF group was furthermore trend-wise correlated with NF-induced ADHD symptom improvements. The findings of this study show, that during error monitoring, fMRI-NF training of rIFC upregulation elicited improvement in post-error behavioural adjustments and concomitant increased activation in left hemispheric fronto-insular-striatal and premotor regions mediating self-control and self-monitoring functions. This suggests that the administration of fMRI-NF of the rIFC may have had an impact on wider networks of self-regulation and self-monitoring in adolescents with ADHD.

1 kHz fixed-target serial crystallography using a multilayer monochromator and an integrating pixel detector.

Reliable sample delivery and efficient use of limited beam time have remained bottlenecks for serial crystallography (SX). Using a high-intensity polychromatic X-ray beam in combination with a newly developed charge-integrating JUNGFRAU detector, we have applied the method of fixed-target SX to collect data at a rate of 1 kHz at a synchrotron-radiation facility. According to our data analysis for the given experimental conditions, only about 3 000 diffraction patterns are required for a high-quality diffraction dataset. With indexing rates of up to 25%, recording of such a dataset takes less than 30 s.

Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays.

The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry. Manipulating the organization around transition metal ions with covalent and supramolecular interactions is a general strategy that underlies most synthetic protocols. Achieving similar control for photoexcited molecular complexes is necessary to advance the design of light-driven functionalities. This objective calls for monitoring the ultrafast dynamics of the primary (1-CS) and the secondary (2-CS) coordination spheres on the atomic scale, which remains to date an important experimental challenge for short-lived species. In this work, transient wide-angle scattering of hard X-rays (25 keV) is employed with state-of-the-art AIMD simulations in order to visualize the 1-CS (solute-only) and the 2-CS (solvation cage) of the photoinduced high-spin (HS) state for [Fe(bpy)3]2+ (bpy = 2,2'-bipyridine) in aqueous solution. Correlating this structural information in real-space reveals the interlacing of the two CS, which in turn explains why solvation affects the photoinduced electronic and structural dynamics in this class of complexes. More generally, these results obtained for a prominent prototypical system in ultrafast X-ray sciences demonstrate the unique perspectives offered by this technique to gain the crucial knowledge about the multiscale solvation dynamics that is currently missing for controlling the solute-solvent interactions in advanced functional nano and biomaterials employed for photoconversion.

Generation of a large compressive strain wave in graphite by ultrashort-pulse laser irradiation.

We have studied strain wave generation in graphite induced by an intense ultrashort laser pulse. The study was performed in the intensity regime above the ablation threshold of graphite. The aim was to maximize the strain and, thus, also the internal pressure (stress). Laser pulses with a 1 ps temporal duration melt the surface of graphite resulting in a molten material which initially exists at the solid density. As the molten material expands, a compressive strain wave starts propagating into the crystal below the molten layer. The strain pulse was studied with time-resolved X-ray diffraction. At a temporal delay of 100 ps after laser excitation, we observed >10% compressive strain, which corresponds to a pressure of 7.2 GPa. This strain could be reproduced by hydrodynamic simulations, which also provided a temperature map as a function of time and depth.

Observation of the shock-induced ß-Sn to b.c.t.-Sn transition using time-resolved X-ray diffraction.

Time-resolved X-ray diffraction measurements have been carried out on dynamically compressed Sn up to a maximum pressure of ∼13 GPa at the European Synchrotron Radiation Facility. The phase transition from ß-Sn to body-centered tetragonal (b.c.t.) Sn has been observed using synchrotron X-ray diffraction for the first time undergoing shock compression and release. Following maximum compression, the sample releases to lower pressures for several nanoseconds until the reverse transition occurs. The data are in good agreement with previous shock boundaries that indicate that the ß-Sn phase is stable ∼2 GPa higher than the static boundary upon compression and the b.c.t.-Sn phase is stable ∼1 GPa lower upon release. The transition to the high-pressure phase reveals a loss of texture in the X-ray diffraction data from the `quasi' single-crystal ß-Sn structure to a more powder-like Debye-Scherrer ring.

Initial metal-metal bond breakage detected by fs X-ray scattering in the photolysis of Ru3(CO)12 in cyclohexane at 400 nm.

Using femtosecond resolution X-ray solution scattering at a free electron laser we were able to directly observe metal-metal bond cleavage upon photolysis at 400 nm of Ru3(CO)12, a prototype for the photochemistry of transition metal carbonyls. This leads to the known single intermediate Ru3(CO)11(µ-CO)*, with a bridging ligand (µCO) and where the asterisk indicates an open Ru3-ring. This loses a CO ligand on a picosecond time scale yielding a newly observed triple bridge intermediate, Ru3(CO)8(µ-CO)3*. This loses another CO ligand to form the previously observed Ru3(CO)10, which returns to Ru3(CO)12via the known single-bridge Ru3(CO)10(µ-CO). These results indicate that contrary to long standing hypotheses, metal-metal bond breakage is the only chemical reaction immediately following the photolysis of Ru3(CO)12 at 400 nm. Combined with previous picosecond resolution X-ray scattering data and time resolved infrared spectroscopy these results yield a new mechanism for the photolysis of Ru3(CO)12.

Functional connectivity changes associated with fMRI neurofeedback of right inferior frontal cortex in adolescents with ADHD.

Attention Deficit Hyperactivity Disorder (ADHD) is associated with poor self-control, underpinned by inferior fronto-striatal deficits. We showed previously that 18 ADHD adolescents over 11 runs of 8.5 min of real-time functional magnetic resonance neurofeedback of the right inferior frontal cortex (rIFC) progressively increased activation in 2 regions of the rIFC which was associated with clinical symptom improvement. In this study, we used functional connectivity analyses to investigate whether fMRI-Neurofeedback of rIFC resulted in dynamic functional connectivity changes in underlying neural networks. Whole-brain seed-based functional connectivity analyses were conducted using the two clusters showing progressively increased activation in rIFC as seed regions to test for changes in functional connectivity before and after 11 fMRI-Neurofeedback runs. Furthermore, we tested whether the resulting functional connectivity changes were associated with clinical symptom improvements and whether they were specific to fMRI-Neurofeedback of rIFC when compared to a control group who had to self-regulate another region. rIFC showed increased positive functional connectivity after relative to before fMRI-Neurofeedback with dorsal caudate and anterior cingulate and increased negative functional connectivity with regions of the default mode network (DMN) such as posterior cingulate and precuneus. Furthermore, the functional connectivity changes were correlated with clinical improvements and the functional connectivity and correlation findings were specific to the rIFC-Neurofeedback group. The findings show for the first time that fMRI-Neurofeedback of a typically dysfunctional frontal region in ADHD adolescents leads to strengthening within fronto-cingulo-striatal networks and to weakening of functional connectivity with posterior DMN regions and that this may be underlying clinical improvement.

XFEL experiments: jitter of pump-probe time delays and pulse intensities.

Jitter of XFEL signals due to fluctuations in shot-to-shot time delays and intensities are explored in the frame of a statistical theory of X-ray diffraction from liquids. Deformed signals are calculated at different levels of pump-probe jitter. A new method is proposed to eliminate these distortions.

Liquid X-ray scattering with a pink-spectrum undulator.

X-ray scattering from a liquid using the spectrum from the undulator fundamental is examined as a function of the bandwidth of the spectrum. The synchrotron-generated X-ray spectrum from an undulator is 'pink', i.e. quasi-monochromatic but having a saw-tooth-shaped spectrum with a bandwidth from 1 to 15%. It is shown that features in S(q) are slightly shifted and dampened compared with strictly monochromatic data. In return, the gain in intensity is 250-500 which makes pink beams very important for time-resolved experiments. The undulator spectrum is described by a single exponential with a low-energy tail. The tail shifts features in the scattering function towards high angles and generates a small reduction in amplitude. The theoretical conclusions are compared with experiments. The r-resolved Fourier transformed signals are discussed next. Passing from q- to r-space requires a sin-Fourier transform. The Warren convergence factor is introduced in this calculation to suppress oscillatory artifacts from the finite qM in the data. It is shown that the deformation of r-resolved signals from the pink spectrum is small compared with that due to the Warren factor. The q-resolved and the r-resolved pink signals thus behave very differently.

Nonequilibrium collective dynamics in photoexcited lipid multilayers by time resolved diffuse x-ray scattering.

We study the nonequilibrium shape fluctuations in fluorescence labeled phospholipid multibilayers composed of the model lipid DOPC and the well-known lipid dye Texas red, driven out of equilibrium by short laser pulses. The temporal evolution of the lipid bilayer undulations after excitation was recorded by time resolved x-ray diffraction. Already at moderate peak intensities (Pp≤10(5) W/cm2), pulsed laser illumination leads to significant changes of the undulation modes in a well-defined lateral wavelength band. The observed phenomena evolve on nano- to microsecond time scales after optical excitation, and can be described in terms of a modulation instability in the lipid multilamellar stack.

Time-resolved investigation of nanometer scale deformations induced by a high flux x-ray beam.

We present results of a time-resolved pump-probe experiment where a Si sample was exposed to an intense 15 keV beam and its surface monitored by measuring the wavefront deformation of a reflected optical laser probe beam. By reconstructing and back propagating the wavefront, the deformed surface can be retrieved for each time step. The dynamics of the heat bump, build-up and relaxation, is followed with a spatial resolution in the nanometer range. The results are interpreted taking into account results of finite element method simulations. Due to its robustness and simplicity this method should find further developments at new x-ray light sources (FEL) or be used to gain understanding on thermo-dynamical behavior of highly excited materials.

Unveiling the timescale of the R-T transition in human hemoglobin.

Time-resolved wide-angle X-ray scattering, a recently developed technique allowing to probe global structural changes of proteins in solution, was used to investigate the kinetics of R-T quaternary transition in human hemoglobin and to systematically compare it to that obtained with time-resolved optical spectroscopy under nearly identical experimental conditions. Our data reveal that the main structural rearrangement associated with the R-T transition takes place approximately 2 mus after the photolysis of hemoglobin at room temperature and neutral pH. This finding suggests that the 20-mus step observed with time-resolved optical spectroscopy corresponds to a small and localized structural change.

Successive dynamical steps of photoinduced switching of a molecular Fe(III) spin-crossover material by time-resolved x-ray diffraction.

We investigate the out-of-equilibrium switching dynamics of a molecular Fe(III) spin-crossover solid triggered by a femtosecond laser flash. The time-resolved x-ray diffraction and optical results show that the dynamics span from subpicosecond local photoswitching followed by volume expansion (nanosecond) and thermal switching (microsecond). We present a physical picture of the consecutive steps in the photoswitching of molecular materials.

Impulsive solvent heating probed by picosecond x-ray diffraction.

The time-resolved diffraction signal from a laser-excited solution has three principal components: the solute-only term, the solute-solvent cross term, and the solvent-only term. The last term is very sensitive to the thermodynamic state of the bulk solvent, which may change during a chemical reaction due to energy transfer from light-absorbing solute molecules to the surrounding solvent molecules and the following relaxation to equilibrium with the environment around the scattering volume. The volume expansion coefficient alpha for a liquid is typically approximately 1 x 10(-3) K(-1), which is about 1000 times greater than for a solid. Hence solvent scattering is a very sensitive on-line thermometer. The decomposition of the scattered x-ray signal has so far been aided by molecular dynamics (MD) simulations, a method capable of simulating the solvent response as well as the solute term and solute/solvent cross terms for the data analysis. Here we present an experimental procedure, applicable to most hydrogen containing solvents, that directly measures the solvent response to a transient temperature rise. The overtone modes of OH stretching and CH3 asymmetric stretching in liquid methanol were excited by near-infrared femtosecond laser pulses at 1.5 and 1.7 microm and the ensuing hydrodynamics, induced by the transfer of heat from a subset of excited CH3OH* to the bulk and the subsequent thermal expansion, were probed by 100 ps x-ray pulses from a synchrotron. The time-resolved data allowed us to extract two key differentials: the change in the solvent diffraction from a temperature change at constant density, seen at a very short time delay approximately 100 ps, and a term from a change in density at constant temperature. The latter term becomes relevant at later times approximately 1 mus when the bulk of liquid expands to accommodate its new temperature at ambient pressure. These two terms are the principal building blocks in the hydrodynamic equation of state, and they are needed in a self-consistent reconstruction of the solvent response during a chemical reaction. We compare the experimental solvent terms with those from MD simulations. The use of experimentally determined solvent differentials greatly improved the quality of global fits when applied to the time-resolved data for C2H4I2 dissolved in methanol.

Recombination of photodissociated iodine: a time-resolved x-ray-diffraction study.

A time-resolved x-ray-diffraction experiment is presented that aims to study the recombination of laser-dissociated iodine molecules dissolved in CCl4. This process is monitored over an extended time interval from pico- to microseconds. The variations of atom-atom distances are probed with a milliangstrom resolution. A recent theory of time-resolved x-ray diffraction is used to analyze the experimental data; it employs the correlation function approach of statistical mechanics. The most striking outcome of this study is the experimental determination of time-dependent I-I atom-atom distribution functions. The structure of the CCl4 solvent changes simultaneously; the solvent thus appears as a reaction partner rather than an inert medium hosting it. Thermal expansion of the system is nonuniform in time, an effect due to the presence of the acoustic horizon. One concludes that a time-resolved x-ray diffraction permits real-time visualization of solvent and solute motions during a chemical reaction.

Ultrafast x-ray diffraction of transient molecular structures in solution.

We report direct structural evidence of the bridged radical (CH2ICH2.) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with approximately 0.01 angstrom spatial resolution and approximately 100 picosecond time resolution: The loss of one iodine atom from C2H4I2 leads to the C-I-C triangular geometry of CH2ICH2.. This transient C2H4I then binds to an iodine atom to form a new species, the C2H4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.

Picosecond x-ray studies of coherent folded acoustic phonons in a multiple quantum well.

Coherent folded acoustic phonons in a multilayered GaSb/InAs epitaxial heterostructure were generated by femtosecond laser pulses and studied by means of ultrafast x-ray diffraction. Coherent phonons excited simultaneously in the fundamental acoustic branch and the first back-folded branch were detected. This represents the first clear evidence for phonon branch folding based directly on the atomic motion to which x-ray diffraction is sensitive. From a comparison of the measured phonon-modulated x-ray reflectivity with simulations, evidence was found for a reduction of the laser penetration depth. This reduction can be explained by the self-modulation of the refractive index due to photogenerated free carriers.

The condom in relation to prevention of sexually transmitted infections and as a contraceptive method in Sweden.

OBJECTIVE: To analyze in detail the latest Swedish population survey regarding condom use in order to gain a deeper knowledge of the characteristics of women and men using or not using condoms at a time when the number of sexually transmitted infections (STIs) had started to increase. METHODS: From a population-based survey of sexual life in Sweden among men and women aged between 18 and 74 years (n = 2810), we investigated the use of condoms in relation to social demographic, lifestyle, sexual and behavioral characteristics. RESULTS: In the age group 18-49 years, every third person had experience of a legal abortion and every fourth had had an STI. Overall, use of condoms was 12% in the whole population and 15% in the age group 18-49 years. Using a condom as a method of contraception, as opposed to other methods, was found to be less frequent in six subgroups: when coitus was less frequent, age above 25 years, among those who had had many partners and those with earlier experience of abortion or STI, as well as having a risky behavior. Using a condom as a preventive against contracting an STI occurred less often in women and men older than 25 years and among those having coitus more frequently. CONCLUSION: Even with good information and easy accessibility to condoms, there are still obstacles to their use. To achieve the aim of safer sexual practice, it is a challenge for the couple as well as for counselors to reason about the advantages and disadvantages of not using a condom. Discussions about attitudes, behavior and gender differences must be continued and emphasized in coming generations, both on the individual and on a societal level, in order to achieve safer sexual practice.

First investigations of the kinetics of the topochemical reaction of p-formyl-trans-cinnamic acid by time-resolved X-ray diffraction.

Under UV irradiation p-formyl-trans-cinnamic acid (p-FCA) crystals in the beta-phase dimerise irreversibly to solid 4,4'-diformyl-beta-truxinic acid. The experimental conditions were chosen in such a way (non-aqueous environment and room temperature) that the product formed is amorphous. The kinetics of this bimolecular reaction, which has not yet been characterised, was investigated by picosecond time-resolved X-ray diffraction. From the experimental results a mechanism for this topochemical reaction is proposed including two observed time constants, one less than 100 ps and another of several seconds. The feasibility of investigating this class of substances by time-resolved X-ray diffraction from third generation synchrotron sources and future free-electron lasers is discussed.