arXiv subjects

Majed Chergui

Publications and source records attributed to Majed Chergui.

At least 19 recordsLinked to original sources

arXiv2026

Light-Stabilized Metastable Electronic State in NiO with Enhanced Orbital Hybridization

Light-driven control of electronic structure in correlated metal oxides offers new opportunities for optimizing materials used in photovoltaic and photoelectrochemical technologies. We show that photoexcitation of NiO, a prototypical transparent semiconductor and hole-transport material, across its charge-transfer gap produces a long-lived metastable state with enhanced Ni 3d-O 2p orbital hybridization. We characterize this state using Ni K-edge X-ray absorption spectroscopy, which probes how structural and electronic changes affect the unoccupied p density of states during continuous and pulsed ultraviolet excitation. Under pulsed excitation, high carrier densities of approximately 10^20 per cubic centimeter generate a state with a lifetime of approximately 600 picoseconds, in which enhanced hybridization coexists with lattice heating. By contrast, continuous ultraviolet irradiation at much lower carrier densities of approximately 10^13 per cubic centimeter stabilizes a similar electronic state with negligible lattice heating, demonstrating that its formation is not solely thermally driven. First-principles DFT+U+V calculations attribute the spectral changes to stronger Ni 3d-O 2p hybridization, which alters the unoccupied Ni 4p states probed by dipole-allowed K-edge transitions. We attribute this change to the dynamic screening of on-site electronic correlations following photoexcitation, which redistributes the charge density. Because orbital hybridization governs carrier transport and charge-transfer energetics, our results identify photoinduced screening as a mechanism for dynamically tuning correlated oxides and suggest new design principles for optoelectronic materials.

cond-mat.mtrl-sci↗

arXiv2026

Train-Resolved Statistical Recovery of Weak SAXS Signals in Liquids at the European XFEL

We present a train-resolved SAXS methodology for recovering weak scattering signals from high-repetition-rate XFEL datasets and apply it to aqueous L-cysteine solutions measured at the European XFEL. Independent scale-plus-offset fitting was performed for matched cysteine and water train pairs, followed by subtraction of transmission-matched water--water controls. The 0.5 M dataset reveals a reproducible sign-changing residual SAXS signal that increases with incident XFEL transmission and remains after removal of detector-wide scaling, additive offsets, and matched water--water control residuals. Convergence and block-averaging analyses show that the residual emerges progressively as independent train pairs are accumulated and exhibits uncertainty scaling close to the expected inverse square-root dependence on N. These results establish a statistically robust transmission-dependent residual SAXS contribution whose microscopic origin remains unresolved, while demonstrating that train-resolved observables combined with matched controls can substantially improve sensitivity to weak scattering signals in high-repetition-rate XFEL experiments.

physics.optics↗

arXiv2026

Spin waves excited by hard x-ray transient gratings

Recent progress in ultrafast x-ray sources helped establish x-rays as an important tool for probing lattice and magnetic dynamics initiated by femtosecond optical pulses. Here, we explore the potential of ultrashort hard x-ray pulses for driving magnetic dynamics. We use a transient grating technique in which a spatially periodic x-ray excitation pattern gives rise to material excitations at a well-defined wave vector, whose dynamics are monitored via diffraction of an optical probe pulse. The excitation of a ferrimagnetic gadolinium bismuth iron garnet film placed in an external tilted magnetic field by x-rays at the Gd L3 edge results in both magnetic and non-magnetic transient gratings whose contributions to the diffracted signal are separated by polarization analysis. We observe the magnetization precession at both longitudinal acoustic and spin wave frequencies. An analysis with the Landau-Lifshitz-Gilbert equation indicates that the magnetization precession is driven by strain resulting from thermal expansion induced by absorbed x-rays. The results establish x-ray transient gratings as a tool for driving coherent phonons and magnons, with the potential of accessing wave vectors across the entire Brillouin zone.

physics.optics↗

arXiv2025

Femtosecond self-diffraction as a measure of the nonlinear response spectrum

Self diffraction is a four-wave mixing process proportional to the square modulus of third-order nonlinearity susceptibility $χ^{(3)}$, which is related to the material's electronic and thermal properties. In this study, we investigate the wavelength dependence of the self-diffracted signal generated by a femtosecond pulsed laser in a dye solution to directly evaluate the electronic third-order nonlinear susceptibility spectrum. By accounting for absorption effects and phase matching conditions, we determine the $\vertχ^{(3)}\vert$ for different concentrations. Experimental results complemented with theoretical predictions, show that in the low absorption and thin sample limits, the signal reproduce the $\vertχ^{(3)}\vert$ spectral profile. These findings demonstrate the feasibility of measuring nonlinear susceptibility spectra arising solely from the bound-electronic response across a wide spectral range and for various compounds.

physics.optics↗

arXiv2025

Linear and nonlinear X-ray spectra of chiral molecules: X-ray Circular Dichroism, Sum- and Difference-Frequency Generation of fenchone and cysteine

Recent advancements in X-ray light sources at synchrotrons and X-ray free-electron lasers (XFELs) present exciting opportunities to probe molecular chirality using novel nonlinear spectroscopies with element-sensitivity. Circular dichroism (CD) and sum- and difference-frequency generation (SFG/DFG) are established techniques for probing molecular asymmetry in optical regime, with SFG/DFG offering unique advantages due to their background-free nature and independence from circularly polarized light sources. Extending them into the X-ray domain provides deeper insights into local structural asymmetries by leveraging the localized nature of core orbitals. In this work, we simulate X-ray absorption spectroscopy (XAS), X-ray circular dichroism (XCD) and nonlinear optical/X-ray SFG and DFG (OX SFG/DFG) signals for two prototypical chiral molecules, fenchone and cysteine. Our multi-reference simulations reproduce experimental data when available and reveal how novel X-ray spectroscopies exploit the site- and element-sensitivity of X-rays to uncover molecular asymmetry. The XCD spectra show strong asymmetries at chiral centers, while distant atoms contribute less. The OX SFG/DFG signals, under fixed resonant optical excitation, strongly depend on core transition and valence excitation energies. This dependence allows us to introduce two-dimensional (2D) chirality-sensitive valence-core spectroscopy, which provides insight into the overlap between valence orbitals and local molecular asymmetry. Finally, our estimates using realistic laser and X-ray pulse parameters demonstrate that such nonlinear experiments are feasible at XFELs, offering a promising tool for investigating the geometric and electronic structures of chiral molecules.

physics.chem-ph↗

arXiv2023

A set-up for Hard X-ray Time-resolved Resonant Inelastic X-ray Scattering at SwissFEL

We present a new set up for resonant inelastic hard X-ray scattering at the Bernina beamline of SwissFEL with energy, momentum, and temporal resolution. The compact R=0.5 m Johann-type spectrometer can be equipped with up to 3 crystal analysers and allows efficient collection of RIXS spectra. Optical pumping for time-resolved studies can be realized with a broad span of optical wavelengths. We demonstrate the performance of the set-up at overall ~180 meV resolution in a study of ground-state and photoexcited (at 400 nm) honeycomb 5d iridate $α$-$\mathrm{Li_2IrO_3}$. Steady-state RIXS spectra at the Iridium ${L_3}$-edge (11.214 keV) have been collected and are in very good agreement with data collected at synchrotrons. The time-resolved RIXS transients (pumped minus unpumped spectra) exhibit changes in the energy-loss region <2 eV, whose features mostly result from the hopping nature of 5d electrons in the honeycomb lattice. These changes are ascribed to modulations of the Ir-to-Ir intersite transition scattering efficiency, which we associate to a transient screening of the on-site Coulomb interaction.

cond-mat.str-el↗

arXiv2023

Band Gap Renormalization at Different Symmetry Points in Perovskites

Using ultrafast broad-band transient absorption (TA) spectroscopy of photo-excited MAPbBr3 thin films with probe continua in the visible and the mid-to-deep-UV ranges, we capture the ultrafast gap renormalization at the fundamental gap situated at the R symmetry point of the Brillouin Zone (BZ) and a higher energy gap at the M point. Global Lifetime analysis, Lifetime density distribution and spectral trace fitting analysis are applied to extract quantitative information. Our work confirms the similarity of the energy gap renormalization at both symmetry points, which rises within the instrument response function (IRF, ~250 fs) and decays in ~400-600 fs times, and an energy red-shift of ~90-150 meV. The ability to monitor different high symmetry points in photoexcited perovskites opens exciting prospects into the characterization of materials, which can be extended to a larger class of materials.

cond-mat.mtrl-sci↗

arXiv2023

Disentangling the Evolution of Electrons and Holes in photoexcited ZnO nanoparticles

The evolution of charge carriers in photoexcited room temperature ZnO nanoparticles in solution is investigated using ultrafast ultraviolet photoluminescence spectroscopy, ultrafast Zn K-edge absorption spectroscopy and ab-initio molecular dynamics (MD) simulations. The photoluminescence is excited at 4.66 eV, well above the band edge, and shows that electron cooling in the conduction band and exciton formation occur in <500 fs, in excellent agreement with theoretical predictions. The X-ray absorption measurements, obtained upon excitation close to the band edge at 3.49 eV, are sensitive to the migration and trapping of holes. They reveal that the 2 ps transient largely reproduces the previously reported transient obtained at 100 ps time delay in synchrotron studies. In addition, the X-ray absorption signal is found to rise in ~1.4 ps, which we attribute to the diffusion of holes through the lattice prior to their trapping at singly-charged oxygen vacancies. Indeed, the MD simulations show that impulsive trapping of holes induces an ultrafast expansion of the cage of Zn atoms in <200 fs, followed by an oscillatory response at a frequency of ~100 cm-1, which corresponds to a phonon mode of the system involving the Zn sub-lattice.

cond-mat.mtrl-sci↗

arXiv2022

Hard X-ray helical dichroism of disordered molecular media

Chirality is a structural property of molecules lacking mirror symmetry that has strong implications in diverse fields, ranging from life to materials sciences. Established spectroscopic methods that are sensitive to chirality, such as circular dichroism (CD), exhibit weak signal contributions on an achiral background. Helical dichroism (HD), which is based on the orbital angular momentum (OAM) of light, offers a new approach to probe molecular chirality, but it has never been demonstrated on disordered samples. Furthermore, in the optical domain the challenge lies in the need to transfer the OAM of the photon to an electron that is localized on an Å-size orbital. Here, we overcome this challenge using hard X-rays with spiral Fresnel zone, which can induce an OAM. We present the first HD spectra of a disordered powder sample of enantiopure molecular complexes of [Fe(4,4'-diMebpy)3]2+ at the iron K-edge (7.1 keV) with OAM-carrying beams. The HD spectra exhibit the expected inversions of signs switching from a left to a right helical wave front or from an enantiomer to the other. The asymmetry ratios for the HD spectra are within one to five percent for OAM beams with topological charges of one and three. These results open a new window into the studies of molecular chirality and its interaction with the orbital angular momentum of light.

physics.chem-ph↗

arXiv2021

Atomic-level description of thermal fluctuations in inorganic lead halide perovskites

The potential of lead-halide perovskites for realistic applications is currently hindered by their limited long-term stability under functional activation. While the role of lattice flexibility in the thermal response of perovskites has become increasingly evident, the description of thermally-induced distortions is still unclear. In this work, we provide a unified picture of thermal activation in CsPbBr3 across length scales, showing that lattice symmetry does not increase at high temperatures. We combine temperature-dependent XRD, Br K-edge XANES, ab initio MD simulations, and calculations of the XANES spectra by first-principles, accounting for both thermal fluctuations and core hole final state effects. We find that the octahedral tilting of the Pb-Br inorganic framework statistically adopts multiple local configurations over time - in the short-range. In turn, the stochastic nature of the local thermal fluctuations uplifts the longer-range periodic octahedral tilting characterizing the low temperature structure, with the statistical mean of the local configurations resulting in a cubic-like time-averaged lattice. These observations can be rationalized in terms of displacive thermal phase transitions through the soft mode model, in which the phonon anharmonicity of the flexible inorganic framework causes the excess free energy surface to change as a function of temperature. Our work demonstrates that the effect of thermal dynamics on the XANES spectra can be effectively described for largely anharmonic systems, provided ab initio MD simulations are performed to determine the dynamically fluctuating structures, and core hole final state effects are included in order to retrieve an accurate XANES line shape. Moreover, it shows that the soft mode model, previously invoked to describe displacive thermal phase transitions in oxide perovskites, carries a more general validity.

cond-mat.mtrl-sci↗

arXiv2021

Hard X-ray Transient Grating Spectroscopy on Bismuth Germanate

Optical-domain Transient Grating (TG) spectroscopy is a versatile background-free four-wave-mixing technique used to probe vibrational, magnetic and electronic degrees of freedom in the time domain. The newly developed coherent X-ray Free Electron Laser sources allow its extension to the X-ray regime. Xrays offer multiple advantages for TG: their large penetration depth allows probing the bulk properties of materials, their element-specificity can address core-excited states, and their short wavelengths create excitation gratings with unprecedented momentum transfer and spatial resolution. We demonstrate for the first time TG excitation in the hard X-ray range at 7.1 keV. In Bismuth Germanate (BGO), the nonresonant TG excitation generates coherent optical phonons detected as a function of time by diffraction of an optical probe pulse. This experiment demonstrates the ability to probe bulk properties of materials and paves the way for ultrafast coherent four-wave-mixing techniques using X-ray probes and involving nanoscale TG spatial periods.

physics.optics↗

arXiv2021

Quantifying Photoinduced Polaronic Distortions in Inorganic Lead Halide Perovskites Nanocrystals

The development of next generation perovskite-based optoelectronic devices relies critically on the understanding of the interaction between charge carriers and the polar lattice in out-of-equilibrium conditions. While it has become increasingly evident for CsPbBr3 perovskites that the Pb-Br framework flexibility plays a key role in their light-activated functionality, the corresponding local structural rearrangement has not yet been unambiguously identified. In this work, we demonstrate that the photoinduced lattice changes in the system are due to a specific polaronic distortion, associated with the activation of a longitudinal optical phonon mode at 18 meV by electron-phonon coupling, and we quantify the associated structural changes with atomic-level precision. Key to this achievement is the combination of time-resolved and temperature-dependent studies at Br K-edge and Pb L3-edge X-ray absorption with refined ab-initio simulations, which fully account for the screened core-hole final state effects on the X-ray absorption spectra. From the temporal kinetics, we show that carrier recombination reversibly unlocks the structural deformation at both Br and Pb sites. The comparison with the temperature-dependent XAS results rules out thermal effects as the primary source of distortion of the Pb-Br bonding motif during photoexcitation. Our work provides a comprehensive description of the CsPbBr3 perovskites photophysics, offering novel insights on the light-induced response of the system and its exceptional optoelectronic properties.

cond-mat.mtrl-sci↗

arXiv2020

Element- and enantiomer-selective visualization of ibuprofen dimer vibrations

In chemistry, biology and materials science, the ability to access interatomic interactions and their dynamical evolution has become possible with the advent of femtosecond lasers. In particular, the observation of vibrational wave packets via optical (UV-visible-IR) spectroscopies has been a major achievement as it can track the motion of nuclei within the system. However, optical spectroscopies only detect the effect of the interatomic vibrations on the global electronic surfaces. New tuneable, pulsed and polarized sources of short-wavelength radiation, such as X-Ray Free electron lasers, can overcome this limitation, allowing for chemical and, of primary importance in biochemistry, enantiomeric selectivity. This selectivity may be complemented by taking into account the chemical shifts of atoms belonging to different molecular moieties

cond-mat.soft↗

arXiv2020

Giant exciton Mott density in anatase TiO2

Elucidating the carrier density at which strongly bound excitons dissociate into a plasma of uncorrelated electron-hole pairs is a central topic in the many-body physics of semiconductors. However, there is a lack of information on the high-density response of excitons absorbing in the near-to-mid ultraviolet, due to the absence of suitable experimental probes in this elusive spectral range. Here, we present a unique combination of many-body perturbation theory and state-of-the-art ultrafast broadband ultraviolet spectroscopy to unveil the interplay between the ultraviolet-absorbing two-dimensional excitons of anatase TiO$_2$ and a sea of electron-hole pairs. We discover that the critical density for the exciton Mott transition in this material is the highest ever reported in semiconductors. These results deepen our knowledge of the exciton Mott transition and pave the route toward the investigation of the exciton phase diagram in a variety of wide-gap insulators.

cond-mat.mtrl-sci↗

arXiv2020

Doming and spin cascade in Ferric Haems: Femtosecond X-ray Absorption and X-ray Emission Studies

The structure-function relationship is at the heart of biology and major protein deformations are correlated to specific functions. In the case of heme proteins, doming is associated with the respiratory function in hemoglobin and myoglobin, while ruffling has been correlated with electron transfer processes, such as in the case of Cytochrome c (Cyt c). The latter has indeed evolved to become an important electron transfer protein in humans. In its ferrous form, it undergoes ligand release and doming upon photoexcitation, but its ferric form does not release the distal ligand, while the return to the ground state has been attributed to thermal relaxation. Here, by combining femtosecond Fe K-edge X-ray absorption near-edge structure (XANES) studies and femtosecond Fe Kalpha and Kbeta X-ray emission spectroscopy (XES), we demonstrate that the photocycle of ferric Cyt c is entirely due to a cascade among excited spin states of the Iron ion, causing the ferric heme to undergo doming, which we identify for the first time. We also argue that this pattern is common to all ferric haems, raising the question of the biological relevance of doming in such proteins.

physics.chem-ph↗

arXiv2020

Femtosecond X-ray emission study of the spin cross-over dynamics in haem proteins

In haemoglobin (consisting of four globular myoglobin-like subunits), the change from the low-spin (LS) hexacoordinated haem to the high spin (HS) pentacoordinated domed form upon ligand detachment and the reverse process upon ligand binding, represent the transition states that ultimately drive the respiratory function. Visible-ultraviolet light has long been used to mimic the ligand release from the haem by photodissociation, while its recombination was monitored using time-resolved infrared to ultraviolet spectroscopic tools. However, these are neither element- nor spin-sensitive. Here we investigate the transition state in the case of Myoglobin-NO (MbNO) using femtosecond Fe Kalpha and Kbeta non-resonant X-ray emission spectroscopy (XES) at an X-ray free-electron laser upon photolysis of the Fe-NO bond. We find that the photoinduced change from the LS (S = 1/2) MbNO to the HS (S = 2) deoxy-myoglobin (deoxyMb) haem occurs in ca. 800 fs, and that it proceeds via an intermediate (S = 1) spin state. The XES observables also show that upon NO recombination to deoxyMb, the return to the planar MbNO ground state is an electronic relaxation from HS to LS taking place in ca. 30 ps. Thus, the entire ligand dissociation-recombination cycle in MbNO is a spin cross-over followed by a reverse spin cross-over process.

physics.chem-ph↗

arXiv2018

Ultrafast X-ray spectroscopy of conical intersections

Ongoing developments in ultrafast X-ray sources offer powerful new means of probing the com- plex non-adiabatically coupled structural and electronic dynamics of photoexcited molecules. These non-Born-Oppenheimer effects are governed by general electronic degeneracies termed conical in- tersections which play a key role, analogous to that of a transition state, in the electronic-nuclear dynamics of excited molecules. Using high level ab initio quantum dynamics simulations, we studied time-resolved X-ray absorption and photoelectron spectroscopy (TRXAS and TRXPS, respectively) of the prototypical unsaturated organic chromophore, ethylene, following excitation to its S2 state. The TRXAS in particular is highly sensitive to all aspects of the ensuing dynamics. These X-ray spectroscopies provide a clear signature of the wavepacket dynamics near conical intersections, related to charge localization effects driven by the nuclear dynamics. Given the ubiquity of charge localization in excited state dynamics, we believe that ultrafast X-ray spectroscopies offer a unique and powerful route to the direct observation of dynamics around conical intersections.

physics.chem-ph↗

arXiv2018

Phonon-Driven Selective Modulation of Exciton Oscillator Strengths in Anatase TiO2 Nanoparticles

The way nuclear motion affects electronic responses has become a very hot topic in materials science. Coherent acoustic phonons can dynamically modify optical, magnetic and mechanical properties at ultrasonic frequencies, with promising applications as sensors and transducers. Here, by means of ultrafast broadband deep-ultraviolet spectroscopy, we demonstrate that coherent acoustic phonons confined in anatase TiO$_2$ nanoparticles can selectively modulate the oscillator strength of the two-dimensional bound excitons supported by the material. We use many-body perturbation-theory calculations to reveal that the deformation potential is the mechanism behind the generation of the observed coherent acoustic wavepackets. Our results offer a route to manipulate and dynamically tune the properties of excitons in the deep-ultraviolet at room temperature.

cond-mat.mes-hall↗