Marta Łabuda

A multiscale computational study combining electronic-structure calculations, molecular dynamics, reaction-network exploration and machine learning provides new insights into the fragmentation chemistry of DHP and its EI mass spectrum.

Electron ionization (EI) mass spectrometry (MS) is a widely used technique for the compound identification and production of spectra. However, incomplete coverage of reference spectral libraries limits reliable analysis of newly characterized molecules. This study presents a hybrid deep learning model for predicting EI-MS spectra directly from molecular structure. The approach combines a graph neural network encoder with a residual neural network decoder, followed by refinement using cross-attention, bidirectional prediction, and probabilistic, chemistry-informed masks. Trained on the NIST14 EI-MS database (≤500 Da), the model achieves strong library matching performance (Recall@10 ≈ 80.8%) and high spectral similarity. The proposed hybrid GNN (Graph Neural Network)-ResNet (Residual Neural Network) model can generate high-quality synthetic EI-MS spectra to supplement existing libraries, potentially reducing the cost and effort of experimental spectrum acquisition. The obtained results demonstrate the potential of data-driven models to augment EI-MS libraries, while highlighting remaining challenges in generalization and spectral uniqueness.

Effective bond breaking in electron transfer from K collisions with C ₆ Cl ₆ .

We propose to combine quantum chemical calculations, statistical mechanical methods, and photoionization and particle collision experiments to unravel the redistribution of internal energy of the furan cation and its dissociation pathways. This approach successfully reproduces the relative intensity of the different fragments as a function of the internal energy of the system in photoelectron–photoion coincidence experiments and the different mass spectra obtained when ions ranging from Ar⁺ to Xe²⁵⁺ or electrons are used in collision experiments. It provides deep insights into the redistribution of the internal energy in the ionized molecule and its influence on the dissociation pathways and resulting charged fragments. The present pilot study demonstrates the efficiency of a statistical exchange of excitation energy among various degrees of freedom of the molecule and proves that the proposed approach is mature to be extended to more complex systems.

The present work focuses on unraveling the collisional processes leading to the fragmentation of the gas-phase furan molecules under the He⁺ and He²⁺ cations impact in the energy range 5–2000 eV. The presence of different mechanisms was identified by the analysis of the optical fragmentation spectra measured using the collision-induced emission spectroscopy (CIES) in conjunction with the ab initio calculations. The measurements of the fragmentation spectra of furan were performed at the different kinetic energies of both cations. In consequence, several excited products were identified by their luminescence. Among them, the emission of helium atoms excited to the 1s4d ¹D₂, ³D_1,2,3 states was recorded. The structure of the furan molecule lacks an He atom. Therefore, observation of its emission lines is spectroscopic evidence of an impact reaction occurring via relocation of the electronic charge between interacting entities. Moreover, the recorded spectra revealed significant variations of relative band intensities of the products along with the change of the projectile charge and its velocity. In particular, at lower velocities of He⁺, the relative cross-sections of dissociation products have prominent resonance-like maxima. In order to elucidate the experimental results, the calculations have been performed by using a high level of quantum chemistry methods. The calculations showed that in both impact systems two collisional processes preceded fragmentation. The first one is an electron transfer from furan molecules to cations that leads to the neutralization and further excitation of the cations. The second mechanism starts from the formation of the He−C₄H₄O^+/2+ temporary clusters before decomposition, and it is responsible for the appearance of the narrow resonances in the relative cross-section curves.

In this study, novel measurements of negative ion formation in neutral potassium-neutral boronic acid collisions are reported in electron transfer experiments. The fragmentation pattern of phenylboronic acid is comprehensively investigated for a wide range of collision energies, i.e., from 10 to 1000 eV in the laboratory frame, allowing some of the most relevant dissociation channels to be probed. These studies were performed in a crossed molecular beam set up using a potassium atom as an electron donor. The negative ions formed in the collision region were mass analysed with a reflectron time-of-flight mass spectrometer. In the unimolecular decomposition of the temporary negative ion, the two most relevant yields were assigned to BO⁻ and BO₂⁻. Moreover, the collision-induced reaction was shown to be selective, i.e., at energies below 100 eV, it mostly formed BO⁻, while at energies above 100 eV, it mostly formed BO₂⁻. In order to further our knowledge on the complex internal reaction mechanisms underlying the influence of the hybridization state of the boron atom, cyclohexylboronic acid was also investigated in the same collision energy range, where the main dissociation channel yielded BO₂⁻. The experimental results for phenyl boronic acid are supported by ab initio theoretical calculations of the lowest unoccupied molecular orbitals (LUMOs) accessed in the collision process.

We present a complete exploration of the different fragmentation mechanisms of furan (C4H4O) operating at low and high energies. Three different theoretical approaches are combined to determine the structure of all possible reaction intermediates, many of them not described in previous studies, and a large number of pathways involving three types of fundamental elementary mechanisms: isomerization, fragmentation and H/H2 loss processes, this last one was not yet explored. Our results are compared with the existing experimental and theoretical investigations for furan fragmentation. At low energies the first processes to appear are isomerization, that always imply the breaking of one C-O bond and ones or several hydrogen transfers, at intermediate energies the fragmentation of the molecular skeleton becomes the most relevant mechanism and H/H2 loss are the dominant processes at high energy, but the three mechanisms are active in very wide energy ranges and therefore at most energies there is a competition among them.

We present the results of recent investigations of charge transfer processes in the collisions of C²⁺ ions with heterocyclic molecules of tetrahydrofuran.