Excitation localization involving dynamic nanoscale distortions is a central aspect of photocatalysis
, quantum materials
and molecular optoelectronics
. Experimental characterization of such ...distortions requires techniques sensitive to the formation of point-defect-like local structural rearrangements in real time. Here, we visualize excitation-induced strain fields in a prototypical member of the lead halide perovskites
via femtosecond resolution diffuse X-ray scattering measurements. This enables momentum-resolved phonon spectroscopy of the locally distorted structure and reveals radially expanding nanometre-scale strain fields associated with the formation and relaxation of polarons in photoexcited perovskites. Quantitative estimates of the magnitude and shape of this polaronic distortion are obtained, providing direct insights into the dynamic structural distortions that occur in these materials
. Optical pump-probe reflection spectroscopy corroborates these results and shows how these large polaronic distortions transiently modify the carrier effective mass, providing a unified picture of the coupled structural and electronic dynamics that underlie the optoelectronic functionality of the hybrid perovskites.
In phase-change memory devices, a material is cycled between glassy and crystalline states. The highly temperature-dependent kinetics of its crystallization process enables application in memory ...technology, but the transition has not been resolved on an atomic scale. Using femtosecond x-ray diffraction and ab initio computer simulations, we determined the time-dependent pair-correlation function of phase-change materials throughout the melt-quenching and crystallization process. We found a liquid-liquid phase transition in the phase-change materials Ag
In
Sb
Te
and Ge
Sb
at 660 and 610 kelvin, respectively. The transition is predominantly caused by the onset of Peierls distortions, the amplitude of which correlates with an increase of the apparent activation energy of diffusivity. This reveals a relationship between atomic structure and kinetics, enabling a systematic optimization of the memory-switching kinetics.
The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be ...treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical Fe(bpy)
compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.
We present an x-ray regenerative amplifier free-electron laser design capable of producing fully coherent hard x-ray pulses across a broad tuning range at a high steady state repetition rate. The ...scheme leverages a strong undulator taper and an apertured diamond output-coupling cavity crystal to produce both high peak and average spectral brightness radiation that is 2 to 3 orders of magnitude greater than conventional single-pass self-amplified spontaneous emission free-electron laser amplifiers. Refractive guiding in the postsaturation regime is found to play a key role in passively controlling the stored cavity power. The scheme is explored both analytically and numerically in the context of the Linac Coherent Light Source II High Energy upgrade.
Ultrafast X-ray scattering is one of the primary tools to track intrinsic crystallographic evolution with atomic accuracy in real time. However, its application to study nonequilibrium structural ...properties at the two-dimensional limit remains a long-standing challenge due to a significant reduction of diffraction volume and complexity of data analysis. Here, we report femtosecond surface X-ray diffraction in combination with crystallographic model-refinement calculations to quantify the ultrafast structural dynamics of monolayer WSe2 crystals supported on a substrate. We found the absorbed optical photon energy is preferably coupled to the in-plane lattice vibrations within one picosecond whereas the out-of-plane lattice vibration amplitude remains unchanged during the first ten picoseconds. The model-assisted fitting suggests an asymmetric intralayer spacing change upon excitation. The observed nonequilibrium anisotropic structural dynamics agrees with first-principles modelling in both real and momentum space, marking the distinct structural dynamics of monolayer crystals from their bulk counterparts.Electron–phonon coupling in a monolayer WSe2 on a substrate is investigated by femtosecond surface X-ray scattering. Counterintuitively, the absorbed optical photon energy is dominantly coupled to the in-plane lattice vibrations within 1 ps.
Crucial to many light-driven processes in transition metal complexes is the absorption and dissipation of energy by 3d electrons. But a detailed understanding of such non-equilibrium excited-state ...dynamics and their interplay with structural changes is challenging: a multitude of excited states and possible transitions result in phenomena too complex to unravel when faced with the indirect sensitivity of optical spectroscopy to spin dynamics and the flux limitations of ultrafast X-ray sources. Such a situation exists for archetypal polypyridyl iron complexes, such as Fe(2,2'-bipyridine)3(2+), where the excited-state charge and spin dynamics involved in the transition from a low- to a high-spin state (spin crossover) have long been a source of interest and controversy. Here we demonstrate that femtosecond resolution X-ray fluorescence spectroscopy, with its sensitivity to spin state, can elucidate the spin crossover dynamics of Fe(2,2'-bipyridine)3(2+) on photoinduced metal-to-ligand charge transfer excitation. We are able to track the charge and spin dynamics, and establish the critical role of intermediate spin states in the crossover mechanism. We anticipate that these capabilities will make our method a valuable tool for mapping in unprecedented detail the fundamental electronic excited-state dynamics that underpin many useful light-triggered molecular phenomena involving 3d transition metal complexes.
Celotno besedilo
Dostopno za:
DOBA, IJS, IZUM, KILJ, KISLJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
X‐ray speckle visibility spectroscopy using X‐ray free‐electron lasers has long been proposed as a probe of fast dynamics in noncrystalline materials. In this paper, numerical modeling is presented ...to show how the data interpretation of visibility spectroscopy can be impacted by the nonidealities of real‐life X‐ray detectors. Using simulated detector data, this work provides a detailed analysis of the systematic errors of several contrast extraction algorithms in the context of low‐count‐rate X‐ray speckle visibility spectroscopy and their origins are discussed. Here, it was found that the finite detector charge cloud and pixel size lead to an unavoidable `degeneracy' in photon position determination, and that the contrasts extracted using different algorithms can all be corrected by a simple linear model. The results suggest that experimental calibration of the correction coefficient at the count rate of interest is possible and essential. This allows computationally lightweight algorithms to be implemented for on‐the‐fly analysis.
A numerical model that can mimic closely the behavior of real X‐ray detectors in the context of X‐ray speckle visibility spectroscopy is described. Using this model, this work investigates the origin of discrepancies between commonly used photon locating algorithms and proposes a calibration routine to resolve the discrepancy.
The X‐ray Pump–Probe instrument achieves femtosecond time‐resolution with hard X‐ray methods using a free‐electron laser source. It covers a photon energy range of 4–24 keV. A femtosecond optical ...laser system is available across a broad spectrum of wavelengths for generating transient states of matter. The instrument is designed to emphasize versatility and the scientific goals encompass ultrafast physical, chemical and biological processes involved in the transformation of matter and transfer of energy at the atomic scale.
X-ray free electron lasers (XFELs) deliver short (<100 fs) and intense (∼1012 photons) pulses of hard X-rays, making them excellent sources for time-resolved studies. Here we show that, despite the ...inherent instabilities of current (SASE based) XFELs, they can be used for measuring high-quality X-ray absorption data and we report femtosecond time-resolved X-ray absorption near-edge spectroscopy (XANES) measurements of a spin-crossover system, iron(II) tris(2,2′-bipyridine) in water. The data indicate that the low-spin to high-spin transition can be modeled by single-exponential kinetics convoluted with the overall time resolution. The resulting time constant is ∼160 fs.
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