arXiv subjects

Wojciech Gawelda

Publications and source records attributed to Wojciech Gawelda.

10 recordsLinked to original sources

arXiv2026

Crystallisation kinetics of supercooled liquid palladium

In this study, we employ classical molecular dynamics (MD) simulations to investigate the crystallisation kinetics of supercooled liquid palladium and relate the results to time-resolved X-ray diffraction measurements on rapidly quenched Pd thin films. Crystal nucleation and growth rates are determined over the temperature range $700$--$1150~\mathrm{K}$ ($0.38$--$0.65 T_{\mathrm{m}}$) by analysing the evolution of the microstructure during the liquid-to-crystal transition. The self-diffusion coefficient of Pd, obtained from the atomic mean-squared displacement, follows Arrhenius behaviour over the investigated temperature range, with an activation energy of $467(6)~\mathrm{meV/atom}$, consistent with available data for supercooled liquid metals. The steady-state homogeneous nucleation rate exhibits a maximum of approximately $4 \times 10^{35}~\mathrm{m^{-3} s^{-1}}$ near $0.5 T_{\mathrm{m}}$. Crystal growth occurs at velocities of the order of metres per second, with a temperature dependence consistent with diffusion-limited Wilson-Frenkel kinetics rather than the collision-limited regime. Based on multiple statistically independent simulations, a time-temperature-transformation (TTT) diagram for crystallisation onset is constructed. The TTT curve exhibits a nose near $0.5 T_{\mathrm{m}}$ and $100~\mathrm{ps}$, corresponding to a critical cooling rate for vitrification on the order of $10^{13}~\mathrm{K s^{-1}}.$ The simulations reproduce the crystallisation onset time and temperature observed in time-resolved X-ray diffraction experiments on optically molten Pd thin films quenched at $5 \times 10^{11}~\mathrm{K s^{-1}}.$ These results indicate that homogeneous, rather than heterogeneous, nucleation governs the achievable supercooling in the experimentally studied films.

cond-mat.mtrl-sci↗

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

Unveiling Zn incorporation in CuInS$_2$ quantum dots: X-ray and optical analysis of doping effects, structural modifications and surface passivation

Quantum dots (QDs) exhibit unique properties arising from their reduced size and quantum confinement effects, including exceptionally bright and tunable photoluminescence. Among these, CuInS$_{2}$ QDs have gained significant attention owing to their remarkable broadband emission, making them highly desirable for various optoelectronic applications requiring efficient luminescent nanomaterials. However, maximizing radiative recombination in CuInS$_{2}$ QDs often necessitates minimizing intragap trap states. A common approach involves the introduction of Zn during the synthesis, which typically promotes the formation of a ZnS shell that passivates the QD surface. Despite its importance, the characterization and quantification of Zn incorporation using conventional techniques, such as optical spectroscopy or electron microscopy, remains challenging. In this study, we utilized X-ray absorption spectroscopy (XAS), in both X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectral ranges, to investigate Zn incorporation into CuInS$_{2}$ QDs with element-specific precision. This approach allowed us to detect the formation of a ZnS surface shell and to resolve the spatial distribution of Zn atoms within the QD lattice, distinguishing between Zn as a substituent, or as an interstitial defect. Additionally, we explored the optical and dynamical properties of CuInS$_{2}$ QDs using time-resolved optical spectroscopies, particularly in the presence of electron and hole acceptors. These results provide deeper insights into the role and effectiveness of the Zn-induced passivating layer, paving the way for optimizing QD performance in photoluminescence applications.

cond-mat.mtrl-sci↗

arXiv2024

Selective tracking of charge carrier dynamics in CuInS2 quantum dots

CuInS2 quantum dots have been studied in a broad range of applications, but despite this, the fine details of their charge carrier dynamics remain a subject of intense debate. Two of the most relevant points of discussion are the hole dynamics and the influence of Cu:In synthesis stoichiometry on them. It has been proposed that Cu-deficiency leads to the formation of Cu2+, affecting the localization of holes into Cu defects. Importantly, it is precisely these confined hole states which are used to explain the interesting photoluminescence properties of CuInS2 quantum dots. We use static X-ray spectroscopy to reveal no evidence for a measurable amount of native Cu2+ states in Cu-deficient samples. Instead, the improved properties of these samples are explained by an increase of crystallinity, reducing the concentration of mid gap states. Furthermore, to understand the charge carrier dynamics, herein we employ ultrafast optical transient absorption, and fluorescence up-conversion spectroscopies in combination with ultrafast X-ray absorption spectroscopy using a hard X-ray free electron laser. We demonstrate that in non-passivated samples, holes are transferred from Cu atoms in sub-picosecond timescales. We assign this transfer to occur towards the thiol-based ligands. Finally, we observe that Cu-deficient samples are more robust against the photothermal heating effects of using higher laser fluences. This is not the case for the stoichiometric sample, where heating effects on the structure are directly observed.

physics.chem-ph↗

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↗

arXiv2023

Ultrafast two-colour X-ray emission spectroscopy reveals excited state landscape in a base metal dyad

Effective photoinduced charge transfer makes molecular bimetallic assemblies attractive for applications as active light induced proton reduction systems. For a more sustainable future, development of competitive base metal dyads is mandatory. However, the electron transfer mechanisms from the photosensitizer to the proton reduction catalyst in base metal dyads remain so far unexplored. We study a Fe-Co dyad that exhibits photocatalytic H2 production activity using femtosecond X-ray emission spectroscopy, complemented by ultrafast optical spectroscopy and theoretical time-dependent DFT calculations, to understand the electronic and structural dynamics after photoexcitation and during the subsequent charge transfer process from the FeII photosensitizer to the cobaloxime catalyst. Using this novel approach, the simultaneous measurement of the transient Kalpha X-ray emission at the iron and cobalt K-edges in a two-colour experiment is enabled making it possible to correlate the excited state dynamics to the electron transfer processes. The methodology, therefore, provides a clear and direct spectroscopic evidence of the Fe->Co electron transfer responsible for the proton reduction activity.

physics.chem-ph↗

arXiv2020

Site-selective and real-time observation of bimolecular electron transfer during photocatalytic water splitting

Time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system for the first time. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [Ir$^{\rm III}$(ppy)$_2$(bpy)]$^+$ photosensitizer, in combination with triethylamine as a sacrificial reductant and Fe$_3$(CO)$_{12}$ as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale. The present findings enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.

physics.chem-ph↗

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↗

arXiv2016

Femtosecond X-Ray Scattering Study of Ultrafast Photoinduced Structural Dynamics in Solvated [Co(terpy)2]2+

We study the structural dynamics of photoexcited [Co(terpy)2]2+ in an aqueous solution with ultrafast x-ray diffuse scattering experiments conducted at the Linac Coherent Light Source. Through direct comparisons with density functional theory calculations, our analysis shows that the photoexcitation event leads to elongation of the Co-N bonds, followed by coherent Co-N bond length oscillations arising from the impulsive excitation of a vibrational mode dominated by the symmetrical stretch of all six Co-N bonds. This mode has a period of 0.33 ps and decays on a subpicosecond time scale. We find that the equilibrium bond-elongated structure of the high spin state is established on a single-picosecond time scale and that this state has a lifetime of ~ 7 ps.

physics.chem-ph↗