Search Results (12)

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies. Full article

This study investigates the structural and optical responses of silica glass to femtosecond (fs) laser irradiation followed by high-energy electron (2.5 MeV, 4.9 GGy) irradiation. Using optical microscopy and spectroscopy techniques, we analyzed retardance, phase shifts, nanograting periodicity, and Raman D₂ band intensity, which is an indicator of local glass densification. S-SNOM and nano-FTIR measurements further revealed changes in the Si–O–Si vibrational bands, indicating partial relaxation of the densified nanolayers under electron irradiation. Our findings reveal significant optical modifications due to subsequent electron irradiation, including reduced retardance and phase values, which are in agreement with the relaxation of the local densification. SEM analysis confirmed the preservation of nanogratings’ morphology including their periodicity. Apart from revealing fundamental aspects related to glass densification within nanogratings, this study also underscores the potential of combined fs-laser and electron irradiation techniques in understanding silica glass behavior under high radiation conditions, which is crucial for applications in harsh environments. Full article

We present an innovative X-ray spectroscopy system to address the complex study of the X-ray emissions arising from laser–target interactions, where the emissions occur within extremely brief intervals from femtoseconds to nanoseconds. Our system combines a Gas Electron Multiplier (GEM) detector with a silicon-based Timepix3 (TPX3) detector. These detectors work in tandem, allowing for a spectroscopic radiation analysis along the same line of sight. With an active area of 10 × 10 cm${}^2$, the GEM detector allows for 1D measurements for X-ray energies (2–50 keV) by utilizing the full 10 cm gas depth. The high-energy part of the radiation beam exits through a downstream side window of the GEM without being absorbed in the gas volume. Positioned side-on at the GEM detector’s exit, the TPX3 detector, equipped with a pixelated sensor (55 µm × 55 µm; active area 14 mm × 14 mm), uses its full 14 mm silicon sensor to detect hard X-rays (50–500 keV) and gamma rays (0.5–10 MeV). We demonstrate the correct operation of the entire detection system and provide a detailed description of the Timepix3 detector’s calibration procedure, highlighting the suitability of the combined system to work in laser plasma facilities. Full article

Electronic coherence signatures can be directly identified in the time–frequency maps measured in two-dimensional electronic spectroscopy (2DES). Here, we demonstrate the theory and discuss the advantages of this approach via the detailed application to the fast-femtosecond beatings of a wide variety of electronic coherences in ensemble dimers of quantum dots (QDs), assembled from QDs of 3 nm in diameter, with 8% size dispersion in diameter. The observed and computed results can be consistently characterized directly in the time–frequency domain by probing the polarization in the 2DES setup. The experimental and computed time–frequency maps are found in very good agreement, and several electronic coherences are characterized at room temperature in solution, before the extensive dephasing due to the size dispersion begins. As compared to the frequency–frequency maps that are commonly used in 2DES, the time–frequency maps allow exploiting electronic coherences without additional post-processing and with fewer 2DES measurements. Towards quantum technology applications, we also report on the modeling of the time–frequency photocurrent response of these electronic coherences, which paves the way to integrating QD devices with classical architectures, thereby enhancing the quantum advantage of such technologies for parallel information processing at room temperature. Full article

Optical-range bulk diffraction nanogratings were fabricated via challenging direct inscription by ultrashort (femtosecond, fs) laser pulses inside heat-shrinkable polymers (thermoplastics) and VHB 4905 elastomer. The inscribed bulk material modifications do not emerge on the polymer surface, being visualized inside the materials by 3D-scanning confocal photoluminescence/Raman microspectroscopy and by the multi-micron penetrating 30-keV electron beam in scanning electron microscopy. The laser-inscribed bulk gratings have multi-micron periods in the pre-stretched material after the second laser inscription step, with their periods continuously reduced down to 350 nm on the third fabrication step, using thermal shrinkage for thermoplastics and elastic properties for elastomers. This three-step process allows facile laser micro-inscription of diffraction patterns and their following controlled scaling down as a whole pattern to pre-determined dimensions. In elastomers, utilizing the initial stress anisotropy, the post-radiation elastic shrinkage along the given axes could be precisely controlled until the 28-nJ threshold fs-laser pulse energy, where elastomer deformation ability is dramatically reduced, producing wrinkled patterns. In thermoplastics, the fs-laser inscription does not affect their heat-shrinkage deformation up to the carbonization threshold. The measured diffraction efficiency of the inscribed gratings increases during the elastic shrinkage for the elastomers and slightly decreases for the thermoplastics. High 10% diffraction efficiency was demonstrated for the VHB 4905 elastomer at the 350 nm grating period. No significant molecular-level structural modifications were observed by Raman micro-spectroscopy in the inscribed bulk gratings in the polymers. This novel few-step method paves the way for facile and robust ultrashort-pulse laser inscription of bulk functional optical elements in polymeric materials for diffraction, holographic and virtual reality devices. Full article

The motions of nuclei in a molecule can be mathematically described by using normal modes of vibration, which form a complete orthonormal basis. Each normal mode describes oscillatory motion at a frequency determined by the momentum of the nuclei. Near equilibrium, it is common to apply the quantum harmonic-oscillator model, whose eigenfunctions intimately involve combinatorics. Each electronic state has distinct force constants; therefore, each normal-mode basis is distinct. Duschinsky proposed a linearized approximation to the transformation between the normal-mode bases of two electronic states using a rotation matrix. The rotation angles are typically obtained by using quantum-chemical computations or via gas-phase spectroscopy measurements. Quantifying the rotation angles in the condensed phase remains a challenge. Here, we apply a two-dimensional harmonic model that includes a Duschinsky rotation to condensed-phase femtosecond coherence spectra (FCS), which are created in transient–absorption spectroscopy measurements through impulsive excitation of coherent vibrational wavepackets. Using the 2D model, we simulate spectra to identify the signatures of Duschinsky rotation. The results suggest that peak multiplicities and asymmetries may be used to quantify the rotation angle, which is a key advance in condensed-phase molecular spectroscopy. Full article

Cyanobacteriochromes (CBCRs) are promising optogenetic tools for their diverse absorption properties with a single compact cofactor-binding domain. We previously uncovered the ultrafast reversible photoswitching dynamics of a red/green photoreceptor AnPixJg2, which binds phycocyanobilin (PCB) that is unavailable in mammalian cells. Biliverdin (BV) is a mammalian cofactor with a similar structure to PCB but exhibits redder absorption. To improve the AnPixJg2 feasibility in mammalian applications, AnPixJg2_BV4 with only four mutations has been engineered to incorporate BV. Herein, we implemented femtosecond transient absorption (fs-TA) and ground state femtosecond stimulated Raman spectroscopy (GS-FSRS) to uncover transient electronic dynamics on molecular time scales and key structural motions responsible for the photoconversion of AnPixJg2_BV4 with PCB (Bpcb) and BV (Bbv) cofactors in comparison with the parent AnPixJg2 (Apcb). Bpcb adopts the same photoconversion scheme as Apcb, while BV4 mutations create a less bulky environment around the cofactor D ring that promotes a faster twist. The engineered Bbv employs a reversible clockwise/counterclockwise photoswitching that requires a two-step twist on ~5 and 35 picosecond (ps) time scales. The primary forward P_fr → P_o transition displays equal amplitude weights between the two processes before reaching a conical intersection. In contrast, the primary reverse P_o → P_fr transition shows a 2:1 weight ratio of the ~35 ps over 5 ps component, implying notable changes to the D-ring-twisting pathway. Moreover, we performed pre-resonance GS-FSRS and quantum calculations to identify the Bbv vibrational marker bands at ~659,797, and 1225 cm⁻¹. These modes reveal a stronger H-bonding network around the BV cofactor A ring with BV4 mutations, corroborating the D-ring-dominant reversible photoswitching pathway in the excited state. Implementation of BV4 mutations in other PCB-binding GAF domains like AnPixJg4, AM1_1870g3, and NpF2164g5 could promote similar efficient reversible photoswitching for more directional bioimaging and optogenetic applications, and inspire other bioengineering advances. Full article

2D Ti-Fe multilayer preparation has been attracting increased interest due to its ability to form intermetallic compounds between metallic titanium and metallic iron thin layers. In particular, the TiFe compound can absorb hydrogen gas at room temperature. We applied femtosecond laser pulses to heat Ti-Fe multilayer structures to promote the appearance of intermetallic compounds and generate surface nanostructuring. The surface pattern, known as Laser Induced Periodic Surface Structures (LIPSS), can accelerate the kinetics of chemical interaction between solid TiFe and gaseous hydrogen. The formation of LIPSS on Ti-Fe multilayered thin films were investigated using of scanning electron microscopy, photo-electron spectroscopy and X-ray diffraction. To explore the thermal response of the multiple layered structure and the mechanisms leading to surface patterning after irradiating the compound with single laser pulses, theoretical simulations were conducted to interpret the experimental observations. Full article

The impact of europium doping on the electronic and structural properties of the topological insulator Bi₂Te₃ is studied in this paper. The crystallographic structure studied by electron diffraction and transmission microscopy confirms that grown by Molecular Beam Epitaxy (MBE) system film with the Eu content of about 3% has a trigonal structure with relatively large monocrystalline grains. The X-ray photoemission spectroscopy indicates that europium in Bi₂Te₃ matrix remains divalent and substitutes bismuth in a Bi₂Te₃ matrix. An exceptional ratio of the photoemission 4d multiplet components in Eu doped film was observed. However, some spatial inhomogeneity at the nanometer scale is revealed. Firstly, local conductivity measurements indicate that the surface conductivity is inhomogeneous and is correlated with a topographic image revealing possible coexistence of conducting surface states with insulating regions. Secondly, Time of Flight Secondary Ion Mass Spectrometry (TOF-SIMS) depth-profiling also shows partial chemical segregation. Such in-depth inhomogeneity has an impact on the lattice dynamics (phonon lifetime) evaluated by femtosecond spectroscopy. This unprecedented set of experimental investigations provides important insights for optimizing the process of growth of high-quality Eu-doped thin films of a Bi₂Te₃ topological insulator. Understanding such complex behaviors at the nanoscale level is a necessary step before considering topological insulator thin films as a component of innovative devices. Full article

The use of aluminum alloy AA2024-T4 (Russian designation D16T) in applications requiring a high strength-to-weight ratio and fatigue resistance such as aircraft fuselage often demands the control and modification of surface properties. A promising route to surface conditioning of Al alloys is laser treatment. In the present work, the formation of ripples and conical microstructures under scanning with femtosecond (fs) laser pulses was investigated. Laser treatment was performed using 250 fs pulses of a 1033 nm Yb:YAG laser. The fluence of the pulses varied from 5 to 33 J/cm². The scanning was repeated from 1 to 5 times for different areas of the sample. Treated areas were evaluated using focused ion beam (FIB)- scanning electron microscopy (SEM) imaging and sectioning, energy-dispersive X-ray (EDX) spectroscopy, atomic force microscopy (AFM), and confocal laser profilometry. The period of laser-induced periodic surface structures (LIPSS) and the average spacing of conical microstructures were deduced from SEM images by FFT. Unevenness of the treated areas was observed that is likely to have been caused by ablation debris. The structural and elemental changes of the material inside the conical microstructures was revealed by FIB-SEM and EDX. The underlying formation mechanisms of observed structures are discussed in this paper. Full article

To directly access the dynamics of electron distribution near the Fermi-surface after plasmon excitation, pump-probe spectroscopy was performed by pumping plasmons on noble-metal films and probing the interband transition. Spectral change in the interband transitions is sensitive to the electron distribution near the Fermi-surface, because it involves the d valence-band to the conduction band transitions and should reflect the k-space distribution dynamics of electrons. For the continuous-wave pump and probe experiment, the plasmon modulation spectra are found to differ from both the current modulation and temperature difference spectra, possibly reflecting signatures of the plasmon wave function. For the femtosecond-pulse pump and probe experiment, the transient spectra agree well with the known spectra upon the excitation of the respective electrons resulting from plasmon relaxation, probably because the lifetime of plasmons is shorter than the pulse duration. Full article

Mixed-stacked organic molecular compounds near the neutral–ionic phase boundary, represented by tetrathiafulvalene-p-chloranil (TTF-CA), show a unique phase transition from a paraelectric neutral (N) phase to a ferroelectric ionic (I) phase when subjected to decreasing temperature or applied pressure, which is called an NI transition. This NI transition can also be induced by photoirradiation, in which case it is known as a prototypical ‘photoinduced phase transition’. In this paper, we focus on the ultrafast electron and molecular dynamics in the transition between the N and I states induced by irradiation by a femtosecond laser pulse and a terahertz electric-field pulse in TTF-CA. In the first half of the paper, we review the photoinduced N-to-I transition in TTF-CA studied by femtosecond-pump-probe reflection spectroscopy. We show that in the early stage of the transition, collective charge transfers occur within 20 fs after the photoirradiation, and microscopic one-dimensional (1D) I domains are produced. These ultrafast I-domain formations are followed by molecular deformations and displacements, which play important roles in the stabilization of photogenerated I domains. In the photoinduced I-to-N transition, microscopic 1D N domains are also produced and stabilized by molecular deformations and displacements. However, the time characteristics of the photoinduced N-to-I and I-to-N transitions in the picosecond time domain are considerably different from each other. In the second half of this paper, we review two phenomena induced by a strong terahertz electric-field pulse in TTF-CA: the modulation of a ferroelectric polarization in the I phase and the generation of a large macroscopic polarization in the N phase. Full article