Elementary processes associated with ionization of liquid water provide a framework for understanding radiation-matter interactions in chemistry and biology. Although numerous studies have been ...conducted on the dynamics of the hydrated electron, its partner arising from ionization of liquid water, H
O
, remains elusive. We used tunable femtosecond soft x-ray pulses from an x-ray free electron laser to reveal the dynamics of the valence hole created by strong-field ionization and to track the primary proton transfer reaction giving rise to the formation of OH. The isolated resonance associated with the valence hole (H
O
/OH) enabled straightforward detection. Molecular dynamics simulations revealed that the x-ray spectra are sensitive to structural dynamics at the ionization site. We found signatures of hydrated-electron dynamics in the x-ray spectrum.
Synthesized Light Transients Wirth, A.; Hassan, M. Th; Grguraš, I. ...
Science (American Association for the Advancement of Science),
10/2011, Letnik:
334, Številka:
6053
Journal Article
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Manipulation of electron dynamics calls for electromagnetic forces that can be confined to and controlled over sub-femtosecond time intervals. Tailored transients of light fields can provide these ...forces. We report on the generation of subcycle field transients spanning the infrared, visible, and ultraviolet frequency regimes with a 1.5-octave three-channel optical field synthesizer and their attosecond sampling. To demonstrate applicability, we field-ionized krypton atoms within a single wave crest and launched a valence-shell electron wavepacket with a well-defined initial phase. Half-cycle field excitation and attosecond probing revealed fine details of atomic-scale electron motion, such as the instantaneous rate of tunneling, the initial charge distribution of a valence-shell wavepacket, the attosecond dynamic shift (instantaneous ac Stark shift) of its energy levels, and its few-femtosecond coherent oscillations.
X-ray free-electron lasers enable the investigation of the structure and dynamics of diverse systems, including atoms, molecules, nanocrystals and single bioparticles, under extreme conditions. Many ...imaging applications that target biological systems and complex materials use hard X-ray pulses with extremely high peak intensities (exceeding 10
watts per square centimetre). However, fundamental investigations have focused mainly on the individual response of atoms and small molecules using soft X-rays with much lower intensities. Studies with intense X-ray pulses have shown that irradiated atoms reach a very high degree of ionization, owing to multiphoton absorption, which in a heteronuclear molecular system occurs predominantly locally on a heavy atom (provided that the absorption cross-section of the heavy atom is considerably larger than those of its neighbours) and is followed by efficient redistribution of the induced charge. In serial femtosecond crystallography of biological objects-an application of X-ray free-electron lasers that greatly enhances our ability to determine protein structure-the ionization of heavy atoms increases the local radiation damage that is seen in the diffraction patterns of these objects and has been suggested as a way of phasing the diffraction data. On the basis of experiments using either soft or less-intense hard X-rays, it is thought that the induced charge and associated radiation damage of atoms in polyatomic molecules can be inferred from the charge that is induced in an isolated atom under otherwise comparable irradiation conditions. Here we show that the femtosecond response of small polyatomic molecules that contain one heavy atom to ultra-intense (with intensities approaching 10
watts per square centimetre), hard (with photon energies of 8.3 kiloelectronvolts) X-ray pulses is qualitatively different: our experimental and modelling results establish that, under these conditions, the ionization of a molecule is considerably enhanced compared to that of an individual heavy atom with the same absorption cross-section. This enhancement is driven by ultrafast charge transfer within the molecule, which refills the core holes that are created in the heavy atom, providing further targets for inner-shell ionization and resulting in the emission of more than 50 electrons during the X-ray pulse. Our results demonstrate that efficient modelling of X-ray-driven processes in complex systems at ultrahigh intensities is feasible.
The structural dynamics of a molecule are determined by the underlying potential energy landscape. Conical intersections are funnels connecting otherwise separate potential energy surfaces. Posited ...almost a century ago
, conical intersections remain the subject of intense scientific interest
. In biology, they have a pivotal role in vision, photosynthesis and DNA stability
. Accurate theoretical methods for examining conical intersections are at present limited to small molecules. Experimental investigations are challenged by the required time resolution and sensitivity. Current structure-dynamical understanding of conical intersections is thus limited to simple molecules with around ten atoms, on timescales of about 100 fs or longer
. Spectroscopy can achieve better time resolutions
, but provides indirect structural information. Here we present few-femtosecond, atomic-resolution videos of photoactive yellow protein, a 2,000-atom protein, passing through a conical intersection. These videos, extracted from experimental data by machine learning, reveal the dynamical trajectories of de-excitation via a conical intersection, yield the key parameters of the conical intersection controlling the de-excitation process and elucidate the topography of the electronic potential energy surfaces involved.
Abstract
We present the first detailed analysis of the ultra-steep spectrum radio halo in the merging galaxy cluster A521, based on upgraded Giant Metrewave Radio telescope observations. The ...combination of radio observations (300–850 MHz) and archival X-ray data provides a new window into the complex physics occurring in this system. When compared to all previous analyses, our sensitive radio images detected the centrally located radio halo emission to a greater extent of ∼1.3 Mpc. A faint extension of the southeastern radio relic has been discovered. We detected another relic, recently discovered by MeerKAT, and coincident with a possible shock front in the X-rays, at the northwest position of the center. We find that the integrated spectrum of the radio halo is well-fitted with a spectral index of −1.86 ± 0.12. A spatially resolved spectral index map revealed the spectral index fluctuations, as well as an outward radial steepening of the average spectral index. The radio and X-ray surface brightness is well correlated for the entire and different subparts of the halo, with sublinear correlation slopes (0.50–0.65). We also found a mild anticorrelation between the spectral index and X-ray surface brightness. Newly detected extensions of the SE relic and the counter relic are consistent with the merger in the plane of the sky.
Understanding molecular femtosecond dynamics under intense X-ray exposure is critical to progress in biomolecular imaging and matter under extreme conditions. Imaging viruses and proteins at an ...atomic spatial scale and on the time scale of atomic motion requires rigorous, quantitative understanding of dynamical effects of intense X-ray exposure. Here we present an experimental and theoretical study of C60 molecules interacting with intense X-ray pulses from a free-electron laser, revealing the influence of processes not previously reported. Our work illustrates the successful use of classical mechanics to describe all moving particles in C60, an approach that scales well to larger systems, for example, biomolecules. Comparisons of the model with experimental data on C60 ion fragmentation show excellent agreement under a variety of laser conditions. The results indicate that this modelling is applicable for X-ray interactions with any extended system, even at higher X-ray dose rates expected with future light sources.
Imaging of the structure of single proteins or other biomolecules with atomic resolution would be enormously beneficial to structural biology. X-ray free-electron lasers generate highly intense and ...ultrashort x-ray pulses, providing a route towards imaging of single molecules with atomic resolution. The information on molecular structure is encoded in the coherent x-ray scattering signal. In contrast to crystallography there are no Bragg reflections in single molecule imaging, which means the coherent scattering is not enhanced. Consequently, a background signal from incoherent scattering deteriorates the quality of the coherent scattering signal. This background signal cannot be easily eliminated because the spectrum of incoherently scattered photons cannot be resolved by usual scattering detectors. We present an ab initio study of incoherent x-ray scattering from individual carbon atoms, including the electronic radiation damage caused by a highly intense x-ray pulse. We find that the coherent scattering pattern suffers from a significant incoherent background signal at high resolution. For high x-ray fluence the background signal becomes even dominating. Finally, based on the atomic scattering patterns, we present an estimation for the average photon count in single molecule imaging at high resolution. By varying the photon energy from 3.5 keV to 15 keV, we find that imaging at higher photon energies may improve the coherent scattering signal quality.
Synopsis The current work provides an elementary explanation of the signals one can obtain in attosecond transient absorption experiments. We perform a perturbative analysis of the transient ...absorption signal as a function of the time delay between the excitation pulse and the dressing pulse. We discuss an unusual kind of experiment, where the information is gained from the absorption spectrum of an attosecond XUV pump pulse, and the probe pulse gives a reference time, allowing to measure the time evolution of a system. We illustrate our concepts through numerical calculations for a model atom.
Intense femtosecond x-ray pulses from free-electron laser sources allow the imaging of individual particles in a single shot. Early experiments at the Linac Coherent Light Source (LCLS) have led to ...rapid progress in the field and, so far, coherent diffractive images have been recorded from biological specimens, aerosols, and quantum systems with a few-tens-of-nanometers resolution. In March 2014, LCLS held a workshop to discuss the scientific and technical challenges for reaching the ultimate goal of atomic resolution with single-shot coherent diffractive imaging. This paper summarizes the workshop findings and presents the roadmap toward reaching atomic resolution, 3D imaging at free-electron laser sources.
Imperfect knowledge of the times at which 'snapshots' of a system are recorded degrades our ability to recover dynamical information, and can scramble the sequence of events. In X-ray free-electron ...lasers, for example, the uncertainty--the so-called timing jitter--between the arrival of an optical trigger ('pump') pulse and a probing X-ray pulse can exceed the length of the X-ray pulse by up to two orders of magnitude, marring the otherwise precise time-resolution capabilities of this class of instruments. The widespread notion that little dynamical information is available on timescales shorter than the timing uncertainty has led to various hardware schemes to reduce timing uncertainty. These schemes are expensive, tend to be specific to one experimental approach and cannot be used when the record was created under ill-defined or uncontrolled conditions such as during geological events. Here we present a data-analytical approach, based on singular-value decomposition and nonlinear Laplacian spectral analysis, that can recover the history and dynamics of a system from a dense collection of noisy snapshots spanning a sufficiently large multiple of the timing uncertainty. The power of the algorithm is demonstrated by extracting the underlying dynamics on the few-femtosecond timescale from noisy experimental X-ray free-electron laser data recorded with 300-femtosecond timing uncertainty. Using a noisy dataset from a pump-probe experiment on the Coulomb explosion of nitrogen molecules, our analysis reveals vibrational wave-packets consisting of components with periods as short as 15 femtoseconds, as well as more rapid changes, which have yet to be fully explored. Our approach can potentially be applied whenever dynamical or historical information is tainted by timing uncertainty.
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