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Linda Young

Publications and source records attributed to Linda Young.

At least 19 recordsLinked to original sources

Graph Neural Network Predictions of Carbon 1s Binding Energies with Near-Experimental Accuracy

Graph neural networks are promising architectures for fast, accurate and transferable predictions of core-electron binding energies, which depend on the local bond environment. Here we present a graph neural network model for predicting carbon 1s core-electron binding energies in organic molecules. The model is trained with multiconfiguration pair-density functional theory on 8637 carbon atoms in 2116 molecules with 4-16 atoms and evaluated against 570 experimental values in 113 different molecules containing 3-45 atoms. Previous work benchmarked a mean absolute error of 0.27 eV to experiment for the training data level of theory [J. Phys. Chem. A 2025, 129, 36, 8419-8431] and the present model demonstrates an experimental evaluation error of 0.33 eV with good size transferability to larger organic molecules. An equivariant graph neural network is benchmarked against its rotationally invariant analogue and a model comprised of the smooth overlap of atomic positions descriptors and kernel ridge regression for training data efficiency and stability to non-equilibrium geometries absent from the training data. All models show good training data efficiency and the graph based models have improved transferability to non-equilibrium geometries. The use of chemically informed, graph-normalized node features reduces the graph neural network's dependence on message passing depth. A case study on the 45 atom avobenzone tautomers demonstrates the model's ability for instant and precise analysis of complex molecules. The software and data are provided by the open-source AugerNet package at https://doi.org/10.5281/zenodo.19689244.

physics.chem-ph

The chemRIXS Instrument for the LCLS-II X-Ray Free Electron Laser

The chemRIXS instrument at the Linac Coherent Light Source offers new opportunities for studying solution-phase systems with time-resolved soft X-ray spectroscopy through the recently commissioned high-repetition-rate LCLS-II X-ray free electron laser. The orders-of-magnitude X-ray flux improvement provided by the superconducting accelerator, combined with corresponding advances in the optical laser system and the liquid jet recirculation system, enables studies on dilute systems with high signal-to-noise compared to what was possible with the LCLS-I copper accelerator. These capabilities open up time-resolved X-ray absorption spectroscopy and resonant inelastic X-ray scattering to entirely new classes of samples, as well as enabling the development of new soft X-ray spectroscopies on liquid samples. An overview of the beamline components and the first LCLS-II commissioning results are presented.

physics.ins-det

Impact of Atomic Substitution on Core-Hole Relaxation Dynamics: A Study of Br$_2$ and IBr

Understanding inner-shell decay processes in heavy-element molecules is essential for unraveling x-ray-induced photodynamics and advancing molecular imaging techniques. In this study, we investigate the influence of atomic substitution on core-hole relaxation dynamics and molecular fragmentation in Br2 and IBr, initiated by x-ray absorption at the Br K-edge. Using a combination of X-ray/ion coincidence measurements and Monte Carlo/molecular dynamics simulations, we track charge distribution and the kinetic energy release (KER) of fragment ions with a total charge from 2+ to 8+. For both molecules, the simulated KER values show good agreement with experiment across different fragmentation channels. Our comparison reveals that substituting Br with the heavier I atom in IBr has minimal impact on the inner-shell electronic decay process, but significantly influences nuclear motion, leading to slower dissociation, thereby a KER close to the Coulomb limit, an effect attributed to the atomic mass. These findings highlight the interplay between electronic and nuclear effects in molecular fragmentation, particularly in heavy-element species, and provide new insights into medical therapies, structural biology, and astrophysics.

physics.atm-clus

Nonlinear reversal of photo-excitation on the attosecond time scale improves ultrafast x-ray diffraction images

The advent of isolated and intense sub-femtosecond X-ray pulses enables tracking of quantummechanical motion of electrons in molecules and solids. The combination of X-ray spectroscopy and diffraction imaging is a powerful approach to visualize non-equilibrium dynamics in systems beyond few atoms. However, extreme x-ray intensities introduce significant electronic damage, limiting material contrast and spatial resolution. Here we show that newly available intense subfemtosecond (sub-fs) x-ray FEL pulses can outrun most ionization cascades and partially reverse x-ray damage through stimulated x-ray emission in the vicinity of a resonance. In our experiment, we compared thousands of coherent x-ray diffraction patterns and simultaneously recorded ion spectra from individual Ne nanoparticles injected into the FEL focus. Our experimental results and theoretical modeling reveal that x-ray diffraction increases and the average charge state decreases in particles exposed to sub-fs pulses compared to those illuminated with 15-femtosecond pulses. Sub-fs exposures outrun most Auger decays and impact ionization processes, and enhance nonlinear effects such as stimulated emission, which cycle bound electrons between different states. These findings demonstrate that intense sub-fs x-ray FEL pulses are transformative for advancing high-resolution imaging and spectroscopy in chemical and material sciences, and open the possibilities of coherent control of the interaction between x-rays and complex specimen beyond few atoms.

physics.optics

Computation of Auger Electron Spectra in Organic Molecules with Multiconfiguration Pair-Density Functional Theory

Efficiently and accurately computing molecular Auger electron spectra for larger systems is limited by the increasing complexity of the scaling in the number of doubly ionized final states with respect to the system size. In this work, we benchmark the application of multiconfiguration pair-density functional theory with a restricted active space (RAS) reference wave function, for computing the carbon K-edge decay spectra of 21 organic molecules, with decay rates computed within the one-center approximation. The performance of different basis sets and on-top functionals is evaluated and the results show that multiconfiguration pair-density functional theory is comparable in accuracy to RAS followed by second-order perturbation theory, but at a significantly reduced cost and both methods demonstrate good agreement with experiment.

physics.chem-ph

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

Attosecond Coherent Electron Motion in a Photoionized Aromatic Molecule

In molecular systems, the ultrafast motion of electrons initiates the process of chemical change. Tracking this electronic motion across molecules requires coupling attosecond time resolution to atomic-scale spatial sensitivity. In this work, we employ a pair of attosecond x-ray pulses from an x-ray free-electron laser to follow electron motion resulting from the sudden removal of an electron from a prototypical aromatic system, para-aminophenol. X-ray absorption enables tracking this motion with atomic-site specificity. Our measurements are compared with state-of-the-art computational modeling, reproducing the observed response across multiple timescales. Sub-femtosecond dynamics are assigned to states undergoing non-radiative decay, while few-femtosecond oscillatory motion is associated with electronic wavepacket motion in stable cation states, that will eventually couple to nuclear motion. Our work provides insight on the ultrafast charge motion preceding and initiating chemical transformations in moderately complex systems, and provides a powerful benchmark for computational models of ultrafast charge motion in matter.

physics.chem-ph

The Auger-Meitner Radioisotope Microscope: an instrument for characterization of Auger electron multiplicities and energy distributions

We describe a new instrument, the Argonne Auger Radioisotope Microscope (ARM), capable of characterizing the Auger electron emission of radionuclides, including candidates relevant in nuclear medicine. Our approach relies on event-by-event ion-electron coincidence, time-of-flight, and spatial readout measurement to determine correlated electron multiplicity and energy distributions of Auger decays. We present a proof-of-principle measurement with the ARM using X-ray photoionization of stable krypton beyond the K-edge and identify a bifurcation in the electron multiplicity distribution depending on the emission of K-LX electrons. Extension of the ARM to the characterization of radioactive sources of Auger electron emissions is enabled by the combination of two recent developments: (1) cryogenic buffer gas beam technology to introduce Auger emitters into the detection region with well-defined initial conditions, and (2) large-area micro-channel plate detectors with multi-hit detection capabilities to simultaneously detect multiple electrons emitted in a single decay. The ARM will generate new experimental data on Auger multiplicities that can be used to benchmark atomic relaxation and decay models. This data will provide insight into the low-energy regime of Auger electrons where intensity calculations are most challenging and experimental data is limited. In particular, accurate multiplicity data of the low-energy regime can be used to inform oncological dosimetry models, where electron energies less than 500 eV are known to be most effective in damaging DNA and cell membranes.

physics.ins-det

Transmission spectroscopy of CF$_4$ molecules in intense x-ray fields

The nonlinear interaction of x-rays with matter is at the heart of understanding and controlling ultrafast molecular dynamics from an atom-specific viewpoint, providing new scientific and analytical opportunities to explore the structure and dynamics of small quantum systems. At increasingly high x-ray intensity, the sensitivity of ultrashort x-ray pulses to specific electronic states and emerging short-lived transient intermediates is of particular relevance for our understanding of fundamental multi-photon absorption processes. In this work, intense x-ray free-electron laser (XFEL) pulses at the European XFEL (EuXFEL) are combined with a gas cell and grating spectrometer for a high-intensity transmission spectroscopy study of multiphoton-induced ultrafast molecular fragmentation dynamics in CF$_4$. This approach unlocks the direct intra-pulse observation of transient fragments, including neutral atoms, by their characteristic absorption lines in the transmitted broad-band x-ray spectrum. The dynamics with and without initially producing fluorine K-shell holes are studied by tuning the central photon energy. The absorption spectra are measured at different FEL intensities to observe nonlinear effects. Transient isolated fluorine atoms and ions are spectroscopically recorded within the ultrashort pulse duration of few tens of femtoseconds. An isosbestic point that signifies the correlated transition between intact neutral CF$_4$ molecules and charged atomic fragments is observed near the fluorine K-edge. The dissociation dynamics and the multiphoton absorption-induced dynamics encoded in the spectra are theoretically interpreted. Overall, this study demonstrates the potential of high-intensity x-ray transmission spectroscopy to study ultrafast molecular dynamics with sensitivity to specific intermediate species and their electronic structure.

physics.atom-ph

Ultrafast Nuclear Dynamics in Double-Core Ionized Water Molecules

Double-core-hole (DCH) states in isolated water and heavy water molecules, resulting from the sequential absorption of two x-ray photons, have been investigated. A comparison of the subsequent Auger emission spectra from the two isotopes provides direct evidence of ultrafast nuclear motion during the 1.5 fs lifetime of these DCH states. Our numerical results align well with the experimental data, providing for various DCH states an in-depth study of the dynamics responsible of the observed isotope effect.

physics.chem-ph

Experimental Demonstration of Attosecond Pump-Probe Spectroscopy with an X-ray Free-Electron Laser

Pump-probe experiments with sub-femtosecond resolution are the key to understanding electronic dynamics in quantum systems. Here we demonstrate the generation and control of sub-femtosecond pulse pairs from a two-colour X-ray free-electron laser (XFEL). By measuring the delay between the two pulses with an angular streaking diagnostic, we characterise the group velocity of the XFEL and demonstrate control of the pulse delay down to 270 as. We demonstrate the application of this technique to a pump-probe measurement in core-excited para-aminophenol. These results demonstrate the ability to perform pump-probe experiments with sub-femtosecond resolution and atomic site specificity.

physics.acc-ph

X-ray induced electron and ion fragmentation dynamics in IBr

Characterization of the inner-shell decay processes in molecules containing heavy elements is key to understanding x-ray damage of molecules and materials and for medical applications with Auger-electron-emitting radionuclides. The 1s hole states of heavy atoms can be produced by absorption of tunable x-rays and the resulting vacancy decays characterized by recording emitted photons, electrons, and ions. The 1s hole states in heavy elements have large x-ray fluorescence yields that transfer the hole to intermediate electron shells that then decay by sequential Auger-electron transitions that increase the ion's charge state until the final state is reached. In molecules the charge is spread across the atomic sites, resulting in dissociation to energetic atomic ions. We have used x-ray/ion coincidence spectroscopy to measure charge states and energies of I$^{q+}$ and Br$^{q'+}$ atomic ions following 1s ionization at the I and Br \textit{K}-edges of IBr. We present the charge states and kinetic energies of the two correlated fragment ions associated with core-excited states produced during the various steps of the cascades. To understand the dynamics leading to the ion data, we develop a computational model that combines Monte-Carlo/Molecular Dynamics simulations with a classical over-the-barrier model to track inner-shell cascades and redistribution of electrons in valence orbitals and nuclear motion of fragments.

physics.atom-ph

Resonant Double-Core Excitations with Ultrafast, Intense Pulses

Intense few-to-sub-femtosecond soft x-ray pulses can produce neutral, two-site excited double-core-hole states by promoting two core electrons to the same unoccupied molecular orbital. We theoretically investigate double nitrogen K-edge excitations of nitrous oxide (N2O) with multiconfigurational electronic structure calculations. We show that the second core-excitation energy is reduced with respect to its ground state value. A site-selective double core-excitation mechanism using intense few-femtosecond x-rays is investigated using time-dependent Schrodinger equation (TDSE) simulations. The subsequent two-step Auger-Meitner and two-electrons-one-electron decay spectra of the double core-excited states are analyzed using a Mulliken population analysis of the multiconfirational wavefunctions. The change in the electron emission lineshape between the absorption of 1 or 2 photons in the resonant core-excitation is predicted by combining this approach with the TDSE simulations. We examine the possibility of resolving the double core-excited states with x-ray pump-probe techniques by calculating the chemical shifts of the core-electron binding energy of the core-excited states and decay products.

physics.chem-ph

Enhanced ultrafast X-ray diffraction by transient resonances

Diffraction-before-destruction imaging with single ultrashort X-ray pulses has the potential to visualise non-equilibrium processes, such as chemical reactions, at the nanoscale with sub-femtosecond resolution in the native environment without the need of crystallization. Here, a nanospecimen partially diffracts a single X-ray flash before sample damage occurs. The structural information of the sample can be reconstructed from the coherent X-ray interference image. State-of-art spatial resolution of such snapshots from individual heavy element nanoparticles is limited to a few nanometers. Further improvement of spatial resolution requires higher image brightness which is ultimately limited by bleaching effects of the sample. We compared snapshots from individual 100 nm Xe nanoparticles as a function of the X-ray pulse duration and incoming X-ray intensity in the vicinity of the Xe M-shell resonance. Surprisingly, images recorded with few femtosecond and sub-femtosecond pulses are up to 10 times brighter than the static linear model predicts. Our Monte-Carlo simulation and statistical analysis of the entire data set confirms these findings and attributes the effect to transient resonances. Our simulation suggests that ultrafast form factor changes during the exposure can increase the brightness of X-ray images by several orders of magnitude. Our study guides the way towards imaging with unprecedented combination of spatial and temporal resolution at the nanoscale.

physics.optics

Ghost-imaging-enhanced non-invasive spectral characterization of stochastic x-ray free-electron-laser pulses

High-intensity ultrashort X-ray free-electron laser (XFEL) pulses are revolutionizing the study of fundamental nonlinear x-ray matter interactions and coupled electronic and nuclear dynamics. To fully exploit the potential of this powerful tool for advanced x-ray spectroscopies, a noninvasive spectral characterization of incident stochastic XFEL pulses with high resolution is a key requirement. Here we present a methodology that combines high-acceptance angle-resolved photoelectron time-of-flight spectroscopy and ghost imaging to enhance the quality of spectral characterization of x-ray free-electron laser pulses. Implementation of this non-invasive high-resolution x-ray diagnostic can greatly benefit the ultrafast x-ray spectroscopy community by functioning as a transparent beamsplitter for applications such as transient absorption spectroscopy in averaging mode as well as covariance-based x-ray nonlinear spectroscopies in single-shot mode where the shot-to-shot fluctuations inherent to a self-amplified spontaneous emission (SASE) XFEL pulse are a powerful asset.

physics.atom-ph

Fluorescence intensity correlation imaging with high resolution and elemental contrast using intense x-ray pulses

We theoretically investigate the fluorescence intensity correlation (FIC) of Ar clusters and Mo-doped iron oxide nanoparticles subjected to intense, femtosecond and sub-femtosecond XFEL pulses for high-resolution and elemental contrast imaging. We present the FIC of {\Ka} and {\Kah} emission in Ar clusters and discuss the impact of sample damage on retrieving high-resolution structural information and compare the obtained structural information with those from the coherent difractive imaging (CDI) approach. We found that, while sub-femtosecond pulses will substantially benefit the CDI approach, few-femtosecond pulses may be sufficient for achieving high-resolution information with FIC. Furthermore, we show that the fluorescence intensity correlation computed from the fluorescence of Mo atoms in Mo-doped iron oxide nanoparticles can be used to image dopant distributions.

physics.atm-clus

Ultraintense, ultrashort pulse x-ray scattering in small molecules

We examine x-ray scattering from an isolated organic molecule from the linear to nonlinear absorptiveregime. In the nonlinear regime, we explore the importance of both the elastic and inelastic channelsand observe the onset of nonlinear behavior as a function of pulse duration and energy. In the linearregime, we test the sensitivity of the scattering signal to molecular bonding and electronic correlationvia calculations using the independent atom model (IAM), Hartree-Fock (HF) and density functionaltheory (DFT). Finally, we describe how coherent x-ray scattering can be used to directly visualizefemtosecond charge transfer and dissociation within a single molecule undergoing x-ray multiphotonabsorption.

physics.chem-ph

Resonant propagation of x-rays from the linear to the nonlinear regime

We present a theoretical study of temporal, spectral, and spatial reshaping of intense, ultrafast x-ray pulses propagating through a resonant medium. Our calculations are based on the solution of a 3D time-dependent Schrödinger-Maxwell equation, with the incident x-ray photon energy on resonance with the core-level 1s-3p transition in neon. We study the evolution of the combined incident and medium-generated field, including the effects of stimulated emission, absorption, ionization and Auger decay, as a function of the input pulse energy and duration. We find that stimulated Raman scattering between core-excited states $1s^{-1}3p$ and $2p^{-1}3p$ occurs at high x-ray intensity, and that the emission around this frequency is strongly enhanced when also including the similar $1s^{-1}-2p^{-1}$ response of the ion. We also explore the dependence of x-ray self-induced transparency (SIT) and self-focusing on the pulse intensity and duration, and we find that the stimulated Raman scattering plays an important role in both effects. Finally, we discuss how these nonlinear effects may potentially be exploited as control parameters for pulse properties of x-ray free-electron laser sources.

physics.atom-ph