Decoupling spin-orbital correlations in a layered manganite amidst ultrafast hybridized charge-transfer band excitation
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75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
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Results for “Ultrafast laser spectroscopy”
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Ultrafast One-Dimensional Peierls-Distortion Dynamics in 1T′−ReS 2 Revealed by 4D Electron Microscopy
Rhenium disulfide (ReS 2 ), a prototypical 2D semiconductor with an anisotropic 1T′ structure due to the pronounced Peierls distortion, has demonstrated great potential for polarization-dependent optoelectronics and photonics. Here, we report an ultrafast phase transition occurring within 1 ps, accompanied by a one-dimensional Peierls-distortion relaxation in 1T′−ReS 2 revealed with combined 4D electron microscopy and time-dependent density functional theory calculations. Upon femtosecond laser pulse excitation, the Re-Re dimerization morphology rapidly transforms from a diamond cluster to zigzag chains and persists for several nanoseconds. Here, this ultrafast Peierls-distortion relaxation is further verified by transient changes in optical anisotropy via polarization-dependent transient absorption spectroscopy. Time-dependent density functional theory calculations attribute this novel phase transition to strong correlation between Peierls distortion and impulsive photoexcited carrier doping, predicting a transient band-gap collapse. This Letter opens up an exciting avenue for ultrafast control of Peierls-distortion-induced anisotropy and the metal-insulator transition in 1T′−ReS 2 .
1T’-ReS2↗
Revealing Parallel Inter‐ and Intra‐Ligand Charge Transfer Dynamics in [Ru(L) 2 (dppz)] 2+ Molecular Lightswitch with N K‐Edge X‐Ray Absorption Spectroscopy
In photoactive metal complexes the localization of photoexcited charges dictates the site of chemical reactivity, but few studies measure the charge redistribution in these systems with spatial precision. Herein, we track the inter- and intra-ligand charge transfer processes that underpin light-driven charge separation in the well-studied “molecular lightswitch” [Ru(bpy) 2 dppz] 2+ (aqueous [Ruthenium II (2,2′-bipyridine)2(dipyrido[3,2-a:2′,3′-c]phenazine)] 2+ [Cl − ] 2 ) by probing the electronic structure of ligand nitrogen atoms in real-time using ultrafast X-ray absorption spectroscopy and first principles calculations. We confirm the localization of excited electron density on the phenazine N atoms of dppz and we newly identify two parallel electron transfer pathways to populate this state. Sub-70 fs electron transfer to the phenazine portion of dppz is observed and attributed to intra-ligand electron transfer following Ru-to-dppz metal-to-ligand charge transfer (MLCT) excitation. This fast charge transfer was not reported in prior ultrafast studies. The slower (ca. 2 ps) charge transfer reported extensively in time-resolved optical absorption and emission studies is reassigned here to inter-ligand electron “hopping” between nearly isoenergetic ligand moieties following Ru-to-bpy MLCT excitation. In conclusion, the results demonstrate much faster charge separation than previously identified in this well-studied system, highlighting how extended azaacene ligand motifs promote the competitive charge transfer processes needed to drive light-driven electron transfer chemistry.
Donor-acceptor systems↗
Effect of lattice excitations on transient near-edge x-ray absorption spectroscopy
Here, time-dependent and constituent-specific spectral changes in soft near-edge x-ray absorption spectroscopy (XAS) of an [Fe/MgO] 8 metal/insulator heterostructure after laser excitation are analyzed at the O K-edge with picosecond time resolution. The oxygen absorption edge of the insulator features a uniform intensity decrease of the fine structure at elevated phononic temperatures, which can be quantified by a simple simulation and fitting procedure presented here. Combining XAS with ultrafast electron diffraction measurements and ab initio calculations demonstrates that the transient intensity changes in XAS can be assigned to a transient lattice temperature. Thus, the sensitivity of transient near-edge XAS to phonons is demonstrated.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Switching of the electron-phonon interaction in 1 T –VSe 2 assisted by hot carriers
We apply an intense infrared laser pulse in order to perturb the electronic and vibrational states in the three-dimensional charge density wave material 1T-VSe 2 . Ultrafast snapshots of the light-induced hot carrier dynamics and nonequilibrium quasiparticle spectral function are collected using time- and angle-resolved photoemission spectroscopy. Furthermore, the hot carrier temperature and time-dependent electronic self-energy are extracted from the time-dependent spectral function, revealing that incoherent electron-phonon interactions heat the lattice above the charge density wave critical temperature on a timescale of (200 ± 40) fs. Density functional perturbation theory calculations establish that the presence of hot carriers alters the overall phonon dispersion and quenches efficient low-energy acoustic phonon scattering channels, which results in a new quasiequilibrium state that is experimentally observed.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
New Constraints on the Melting Temperature and Phase Stability of Shocked Iron up to 270 GPa Probed by Ultrafast X-Ray Absorption Spectroscopy
Studying the properties and phase diagram of iron at high-pressure and high-temperature conditions has relevant implications for Earth’s inner structure and dynamics and the temperature of the inner core boundary (ICB) at 330 GPa. Also, a hexagonal-closed packed to body-centered cubic (bcc) phase transition has been predicted by many theoretical works but observed only in a few experiments. The recent coupling of high-power laser with advanced x-ray sources from synchrotrons allows for novel approaches to address these issues. Here, we present a study on shock compressed iron up to 270 GPa and 5800 K probed by single-pulse (100 ps FWHM) x-ray absorption spectroscopy (XAS). Based on the analysis of the XAS spectra, we provide structural identification and bulk temperature measurements along the Hugoniot up to the melting. These results rule out the predicted transition to a high-temperature bcc phase and allow one to discriminate among existing equations of state models and melting curves. In particular, we report the first bulk temperature measurement in shock compressed iron on the melting plateau at 240(20) GPa and 5345(600) K. The melting curve resulting from our work extrapolates to a temperature of 6202(514) K at 330 GPa and represents a refined upper bound for the ICB temperature. Published by the American Physical Society 2024
Balugani, S.↗
Hidden domain boundary dynamics toward crystalline perfection
A central paradigm of nonequilibrium physics concerns the dynamics of heterogeneity and disorder, impacting processes ranging from the behavior of glasses to the emergent functionality of active matter. Understanding these complex mesoscopic systems requires probing the microscopic trajectories associated with irreversible processes, the role of fluctuations and entropy growth, and the timescales on which nonequilibrium responses are ultimately maintained. Approaches that illuminate these processes in model systems may enable a more general understanding of other heterogeneous nonequilibrium phenomena, and potentially define ultimate speed and energy cost limits for information processing technologies. Here, we apply ultrafast single-shot X-ray photon correlation spectroscopy to resolve the nonequilibrium, heterogeneous, and irreversible mesoscale dynamics during a light-induced phase transition in a (PbTiO 3 ) 16 /(SrTiO 3 ) 16 superlattice. Such ferroelectric superlattice systems are a useful platform to study phase transitions and topological dynamics due to their high degree of tunability. This provides an approach for capturing the nucleation of the light-induced phase, the formation of transient mesoscale defects at the boundaries of the nuclei, and the eventual annihilation of these defects, even in systems with complex polarization topologies. We identify a nonequilibrium correlation response spanning >10 orders of magnitude in timescales, with multistep behavior similar to the plateaus observed in supercooled liquids and glasses. We further show how the observed time-dependent long-time correlations can be understood in terms of stochastic and non-Markovian dynamics of domain walls, encoded in waiting-time distributions with power-law tails. This work defines possibilities for probing the nonequilibrium and correlated dynamics of disordered and heterogeneous media.
36 MATERIALS SCIENCE↗
Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy
Excited state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specic and enables direct, individual probes of the proton donating and accepting atoms. Here, we report a computational study to resolve the ESIPT in 10-Hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound, using time-dependent density functional theory combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Overall, our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge paving the way for future experiments at X-ray free electron lasers.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Chirped Laser Pulse Control of Vibronic Wavepackets and Energy Transfer in Phycocyanin 645
Photosynthetic organisms use light-harvesting complexes to increase the spectrum of light that they absorb from solar photons. Recent ultrafast spectroscopic studies have revealed that efficient (sub-ps) energy transfer is mediated by vibronic coherence in the phycobiliprotein phycocyanin 645 (PC645). Here, we report studies that employ broadband pump–probe spectroscopy with linearly chirped excitation pulses to further investigate the relationship between vibronic state preparation and energy transfer dynamics in PC645. Negatively chirped pulse excitation is found to enhance wavepackets of a high-frequency mode (1580 cm –1 ) and increase the rate of downhill energy transfer, while on the other hand, positively chirped pulses suppress these oscillatory features and decrease this rate. Model calculations incorporating the influence of the chirped pump pulse are used to understand its effect on initial state preparation. Furthermore, these results provide mechanistic insight into how the overall nonequilibrium rate of energy transfer is influenced by initial state preparation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultrafast X-Ray Probes of Elementary Molecular Events
Elementary events that determine photochemical outcomes and molecular functionalities happen on the femtosecond and subfemtosecond timescales. Among the most ubiquitous events are the nonadiabatic dynamics taking place at conical intersections. These facilitate ultrafast, nonradiative transitions between electronic states in molecules that can outcompete slower relaxation mechanisms such as fluorescence. The rise of ultrafast X-ray sources, which provide intense light pulses with ever-shorter durations and larger observation bandwidths, has fundamentally revolutionized our spectroscopic capabilities to detect conical intersections. Recent theoretical studies have demonstrated an entirely new signature emerging once a molecule traverses a conical intersection, giving detailed insights into the coupled nuclear and electronic motions that underlie, facilitate, and ultimately determine the ultrafast molecular dynamics. Following a summary of current sources and experiments, we survey these techniques and provide a unified overview of their capabilities. We discuss their potential to dramatically increase our understanding of ultrafast photochemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Low-divergence femtosecond X-ray pulses from a passive plasma lens
Electron and X-ray beams originating from compact laser-wakefield accelerators have very small source sizes that are typically on the micrometre scale. Therefore, the beam divergences are relatively high, which makes it difficult to preserve their high quality during transport to applications. To improve on this, tremendous efforts have been invested in controlling the divergence of the electron beams, but no mechanism for generating collimated X-ray beams has yet been demonstrated experimentally. Here we propose and realize a scheme where electron bunches undergoing focusing in a dense, passive plasma lens can emit X-ray pulses with divergences approaching the incoherent limit. Furthermore, compared with conventional betatron emission, the divergence of this so-called plasma lens radiation is reduced by more than an order of magnitude in solid angle, while maintaining a similar number of emitted photons per electron. This X-ray source offers the possibility of producing brilliant and collimated few-femtosecond X-ray pulses for ultra-fast science, in particular for studies based on X-ray diffraction and absorption spectroscopy.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Demonstration of full-scale spatiotemporal diagnostics of solid-density plasmas driven by an ultra-short relativistic laser pulse using an X-ray free-electron laser
Understanding the complex plasma dynamics in ultra-intense relativistic laser–solid interactions is of fundamental importance for applications of laser–plasma-based particle accelerators, the creation of high-energy-density matter, understanding planetary science, and laser-driven fusion energy. However, experimental efforts in this regime have been limited by the lack of accessibility of over-critical densities and the poor spatiotemporal resolution of conventional diagnostics. Over the last decade, the advent of femtosecond brilliant hard X-ray free-electron lasers (XFELs) has opened new horizons to overcome these limitations. Here, for the first time, we present full-scale spatiotemporal measurements of solid-density plasma dynamics, including preplasma generation with tens of nanometer scale length driven by the leading edge of a relativistic laser pulse, ultrafast heating and ionization at the main pulse arrival, the laser-driven blast wave, and transient surface return current-induced compression dynamics up to hundreds of picoseconds after interaction. These observations are enabled by utilizing a novel combination of advanced X-ray diagnostics including small-angle X-ray scattering, resonant X-ray emission spectroscopy, and propagation-based X-ray phase-contrast imaging simultaneously at the European XFEL-HED beamline station.
Huang, Lingen [Helmholtz-Zentrum Dresden-Rossendor↗
Extended X-ray absorption spectroscopy using an ultrashort pulse laboratory-scale laser-plasma accelerator
Laser-driven compact particle accelerators can provide ultrashort pulses of broadband X-rays, well suited for undertaking X-ray absorption spectroscopy measurements on a femtosecond timescale. Here the Extended X-ray Absorption Fine Structure (EXAFS) features of the K-edge of a copper sample have been observed over a 250 eV window in a single shot using a laser wakefield accelerator, providing information on both the electronic and ionic structure simultaneously. This capability will allow the investigation of ultrafast processes, and in particular, probing high-energy-density matter and physics far-from-equilibrium where the sample refresh rate is slow and shot number is limited. For example, states that replicate the tremendous pressures and temperatures of planetary bodies or the conditions inside nuclear fusion reactions. Using high-power lasers to pump these samples also has the advantage of being inherently synchronised to the laser-driven X-ray probe. A perspective on the additional strengths of a laboratory-based ultrafast X-ray absorption source is presented.
43 PARTICLE ACCELERATORS↗
Characterization of a LaB6 tip as a thermionically enhanced photoemitter
There is a widespread interest in time-resolved electron spectroscopies such as ultrafast electron diffraction, ultrafast electron microscopy, and ultrafast electron energy loss spectroscopy. These techniques require pulsed electron beams with both high current and brightness. LaB6 is commonly used as a thermionic emitter because of its low work function and high electron yield. However, its use as a pulsed photocathode has not been widely explored. Here, we present measurements of the electron yield from a LaB6 filament exposed to 392 nm UV ultrafast laser pulses under a wide range of filament temperatures. We find that sample heating strongly enhances photoelectron yield, an effect known as thermionically enhanced photoemission. However, it also creates potentially undesirable, continuous thermionic background. We conclude that the ideal optimal operating conditions strongly depend on the type of measurement and require defining and quantifying an appropriate figure of merit.
Physics↗
Attosecond Time-Domain Measurement of Core-Level-Exciton Decay in Magnesium Oxide
Excitation of ionic solids with extreme ultraviolet pulses creates localized core-level excitons, which in some cases couple strongly to the lattice. In this paper, core-level-exciton states of magnesium oxide are studied in the time domain at the Mg L 2 , 3 edge with attosecond transient reflectivity spectroscopy. Attosecond pulses trigger the excitation of these short-lived quasiparticles, whose decay is perturbed by time-delayed near-infrared pulses. Combined with a few-state theoretical model, this reveals that the infrared pulse shifts the energy of bright (dipole-allowed) core-level-exciton states as well as induces features arising from dark core-level excitons. We report coherence lifetimes for the two lowest core-level excitons of 2.3 ± 0.2 and 1.6 ± 0.5 fs and show that these are primarily a consequence of strong exciton-phonon coupling, disclosing the drastic influence of structural effects in this ultrafast relaxation process.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Mechanisms of ultrafast GHz burst fs laser ablation
Gigahertz (GHz) femtosecond (fs) lasers have opened possibilities for enhancing and controlling the laser machining quality to engineer the physicochemical properties of materials. However, fundamental understanding of laser-material interactions by GHz fs laser has remained unsolved due to the complexity of associated ablation dynamics. Here, we study the ablation dynamics of copper (Cu) by GHz fs bursts using in situ multimodal diagnostics, time-resolved scattering imaging, emission imaging, and emission spectroscopy. A combination of probing techniques reveals that GHz fs bursts rapidly remove molten Cu from the irradiated spot due to the recoil pressure exerted by following fs pulses. Material ejection essentially stops right after the burst irradiation due to the limited amount of remnant matter, combined with the suppressed heat conduction into the target material. Our work provides insights into the complex ablation mechanisms incurred by GHz fs bursts, which are critical in selecting optimal laser conditions in cross-cutting processing, micro/nano-fabrication, and spectroscopy applications.
47 OTHER INSTRUMENTATION↗
Ultrafast disruptive probing: Simultaneously keeping track of tens of reaction pathways
Ultrafast science depends on different implementations of the well-known pump–probe method. Here, we provide a formal description of ultrafast disruptive probing, a method in which the probe pulse disrupts a transient species that may be a metastable ion or a transient state of matter. Disruptive probing has the advantage of allowing for simultaneous tracking of the yield of tens of different processes. Our presentation includes a numerical model and experimental data on multiple products resulting from the strong-field ionization of two different molecules, partially deuterated methanol and norbornene. The correlated enhancement and depletion signals between all the different fragmentation channels offer comprehensive information on photochemical reaction pathways. In combination with ion imaging and/or coincidence momentum imaging or as complementary to atom-specific probing or ultrafast diffraction methods, disruptive probing is a particularly powerful tool for the study of strong-field laser–matter interactions.
47 OTHER INSTRUMENTATION↗
Femtosecond ultraviolet laser absorption spectroscopy for simultaneous measurements of temperature and OH concentration
This Letter reports a femtosecond ultraviolet laser absorption spectroscopy (fs-UV-LAS) for simultaneous in situ measurements of temperature and species. Here, this fs-UV-LAS technique was demonstrated based on X 2 Π-A 2 Σ + transitions of OH radicals near 308 nm generated in low temperature plasmas and flames. The fs-UV-LAS technique has revealed three major diagnostic benefits. First, a series of absorption features within a spectral bandwidth of ~3.2 nm near 308 nm were simultaneously measured and then enabled simultaneous multi-parameter measurements with enhanced accuracy. The results show that the temperature and OH concentration could be measured with accuracy enhanced by 29–88% and 58–91%, respectively, compared to those obtained with past two-narrow-line absorption methods. Second, an ultrafast time resolution of ~120 picoseconds was accomplished for the measurements. Third, due to the large OH X 2 Π-A 2 Σ + transitions in the UV range, a simple single-pass absorption with a 3-cm path length was allowed for measurements in plasmas with low OH number density down to ~2 × 10 13 cm –3 . Also due to the large OH UV transitions, single-shot fs absorption measurements were accomplished in flames, which was expected to offer more insights into chemically reactive flow dynamics.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗