arXiv subjects

Noelle Walsh

Publications and source records attributed to Noelle Walsh.

5 recordsLinked to original sources

arXiv2025

Multiple charge transfer driven complex reaction dynamics: covalent bonding meets van der Waals interactions

Ultrafast charge transfer (CT) processes redistribute electronic charge within and between molecular units and play a central role in many physical, chemical, and biological phenomena. However, the microscopic pathways of multiple CT events, including the coupled structural evolution and energy redistribution, are challenging to disentangle experimentally in complex systems. To obtain controlled insight into such dynamics, well-defined properties are required. Here, we investigate the N2Ar dimer, which combines a covalent bond with a weak van der Waals interaction, using site-selective synchrotron photoionization and coincident detection of electrons and ions. Combined with ab initio calculations, this approach enables step-by-step tracking of ultrafast CT and fragmentation dynamics. We find that the dimer's structural evolution triggers a second CT event, opening complex reaction pathways in which electrons are transferred back and forth between Ar and N2, through two nonadiabatic transitions involving conical intersections. These results demonstrate that sequential multiple CT-induced transitions, even in a simple dimer, provide controlled insight into nonadiabatic reaction mechanisms relevant to complex systems.

physics.chem-ph↗

arXiv2024

SPRING: an effective and reliable framework for image reconstruction in single-particle Coherent Diffraction Imaging

Coherent Diffraction Imaging (CDI) is an experimental technique to gain images of isolated structures by recording the light scattered off the sample. In principle, the sample density can be recovered from the scattered light field through a straightforward Fourier Transform operation. However, only the amplitude of the field is recorded, while the phase is lost during the measurement process and has to be retrieved by means of suitable, well-established phase retrieval algorithms. In this work, we present SPRING, an analysis framework tailored to X-ray Free Electron Laser (XFEL) single-shot single-particle diffraction data that implements the Memetic Phase Retrieval method to mitigate the shortcomings of conventional algorithms. We benchmark the approach on experimental data acquired in two experimental campaigns at SwissFEL and European XFEL. Imaging results on isolated nanostructures reveal unprecedented stability and resilience of the algorithm's behavior on the input parameters, as well as the capability of identifying the solution in conditions hardly treatable so far with conventional methods. A user-friendly implementation of SPRING is released as open-source software, aiming at being a reference tool for the coherent diffraction imaging community at XFEL and synchrotron facilities.

physics.optics↗

arXiv2024

Site- and Energy-Selective Low-Energy Electron Emission by X-Rays in Aqueous Phase

Low-energy-electron emission from resonant Auger final states via intermolecular Coulombic decay (RA-ICD) has been previously described as a promising scenario for controlling radiation damage for medical purposes, but has so far only been observed in prototypical atomic and molecular van der Waals dimers and clusters. Here, we report the experimental observation of RA-ICD in aqueous solution. We show that for solvated Ca$^{2+}$ ions, the emission can be very efficiently controlled by tuning the photon energy of exciting X-rays to inner-shell resonances of the ions. Our results provide the next step from proving RA-ICD in relatively simple prototype systems to understanding the relevance and potential applications of ICD in real-life scenarios.

physics.chem-ph↗

arXiv2021

Fission of charged nano-hydrated ammonia clusters -- microscopic insights on the nucleation processes

While largely studied on the macroscopic scale, the dynamics leading to nucleation and fission processes in atmospheric aerosols are still poorly understood at the molecular level. Here, we present a joint experimental-theoretical study of a model system consisting of hydrogen-bonded ammonia and water molecules. Experimentally, the clusters were produced via adiabatic co-expansion. Double ionization ionic products were prepared using synchrotron radiation and analyzed with coincident mass- and 3D momentum spectroscopy. Calculations were carried out using ab initio molecular dynamics to understand the fragmentation within the first 500 fs. Further exploration of the potential energy surfaces were performed at a DFT level of theory to gain information on the energetics of the processes. Water was identified as an efficient nano-droplet stabilizer, and is found to have a significant effect even at low water content. On the molecular level, the stabilizing role of water can be related to an increase in the dissociation energy between ammonia molecules and the water enriched environment at the cluster surface. Furthermore, our results support the role of ammonium as a charge carrier in the solution, preferentially bound to surrounding ammonia molecules, which can influence atmospheric nucleation process.

physics.atm-clus↗

arXiv2017

The role of charge and proton transfer in fragmentation of hydrogen-bonded nanosystems: the breakup of ammonia clusters upon single photon multi-ionization

The charge and proton dynamics in hydrogen-bonded networks are investigated using ammonia as a model system. The fragmentation dynamics of medium-sized clusters (1-2 nm) upon single photon multi-ionization is studied, by analyzing the momenta of small ionic fragments. The observed fragmentation pattern of the doubly- and triply- charged clusters reveals a spatial anisotropy of emission between fragments (back-to-back). Protonated fragments exhibit a distinct kinematic correlation, indicating a delay between ionization and fragmentation (fission). The different kinematics observed for channels containing protonated and unprotonated species provides possible insights into the prime mechanisms of charge and proton transfer, as well as proton hopping, in such a nanoscale system.

physics.atm-clus↗