Unveiling the electron-induced ionization cross sections and fragmentation mechanisms of 3,4-dihydro-2H-pyran.

The interactions of electrons with molecular systems under various conditions are essential to interdisciplinary research fields extending over the fundamental and applied sciences. In particular, investigating electron-induced ionization and dissociation of molecules may shed light on the radiation damage to living cells, the physicochemical processes in interstellar environments, and reaction mechanisms occurring in combustion or plasma. We have, therefore, studied electron-induced ionization and dissociation of the gas phase 3,4-dihydro-2H-pyran (DHP), a cyclic ether appearing to be a viable moiety for developing efficient clinical pharmacokinetics and revealing the mechanisms of biofuel combustion. The mass spectra in the m/z = 10-90 mass range were measured at several different energies of the ionizing electron beam using mass spectrometry. The mass spectra of DHP at the same energies were simulated using on-the-fly semi-classical molecular dynamics (MD) within the framework of the QCxMS formalism. The MD settings were suitably adjusted until a good agreement with the experimental mass spectra intensities was achieved, thus enabling a reliable assignment of cations and unraveling the plausible fragmentation channels. Based on the measurement of the absolute total ionization cross section of DHP (18.1 ± 0.9) × 10-16 cm2 at 100 eV energy, the absolute total and partial ionization cross sections of DHP were determined in the 5-140 eV electron energy. Moreover, a machine learning algorithm that was trained with measured cross sections from 25 different molecules was used to predict the total ionization cross section for DHP. Comparison of the machine learning simulation with the measured data showed acceptable agreement, similar to that achieved in past predictions of the algorithm.

Two-body dissociation of isoxazole following double photoionization - an experimental PEPIPICO and theoretical DFT and MP2 study.

The dissociative double photoionization of isoxazole molecules has been investigated experimentally and theoretically. The experiment has been carried out in the 27.5-36 eV photon energy range using vacuum ultraviolet (VUV) synchrotron radiation excitation combined with ion time-of-flight (TOF) spectrometry and photoelectron-photoion-photoion coincidence (PEPIPICO) technique. Five well-resolved two-body dissociation channels have been identified in the isoxazole's coincidence maps, and their appearance energies have been determined. The coincidence yield curves of these dissociation channels have been obtained in the photon energy ranges from their appearance energies up to 36 eV. The double photoionization of isoxazole produces a C3H3NO2+ transient dication, which decomposes into fragments differing from previously reported photofragmentation products of isoxazole. We have found no evidence of pathways leading to the C3H2NO+, HCN+, C2H2O+, C3HN+, or C2H2+ fragments or their neutral counterparts that have been observed in previous neutral photodissociation and single photoionization studies. Instead, the dissociation of isoxazole after the ejection of two electrons is bond-selective and is governed by two reactions, HCO+ + H2CCN+ and H2CO+ + HCCN+, whose appearance energies are 28.6 (±0.3) and 29.4 (±0.3) eV, respectively. A third dissociation channel turns out to be a variant of the most intense channel (HCO+ + H2CCN+), where one of the fragment ions contains a heavy isotope. Two minor dissociation channels occurring at higher energies, CO+ + CH3CN+ and CN+ + H3CCO+, are also identified. The density functional and ab initio quantum chemical calculations have been performed to elucidate the dissociative charge-separating mechanisms and determine the energies of the observed photoproducts. The present work unravels hitherto unexplored photodissociation mechanisms of isoxazole and thus provides deeper insight into the photophysics of five-membered heterocyclic molecules containing two heteroatoms.

Soft X-ray Induced Production of Neutral Fragments in High-Rydberg States at the O 1s Ionization Threshold of the Water Molecule.

Dissociation of water molecules after soft X-ray absorption can yield neutral fragments in high-Rydberg (HR) states. We have studied the production of such fragments by field ionization and ion time-of-flight (TOF) spectrometry. Neutral HR fragments are created at all resonances below the O 1s ionization potential (IP) and particularly within 1 eV above the O 1s IP. The latter effect is due to the recapture of the O 1s photoelectrons into HR orbitals of the molecular water ion after the emission of a fast Auger electron. H2O+(HR) fragments subsequently dissociate, yielding neutral H(HR) and O(HR) fragments, as were found by measuring the TOF spectra by pulsed field ionization. Such measurements were carried out at the O 1s → 4a1 and 2b2 resonances as well as just above the O 1s IP. The TOF spectra also reveal two series of oscillatory structures that are attributed to quantum beats involving Lyman emission in one of the series and field ionization of H(HR) fragments in the other series.

Neutral Dissociation of Pyridine Evoked by Irradiation of Ionized Atomic and Molecular Hydrogen Beams.

The interactions of ions with molecules and the determination of their dissociation patterns are challenging endeavors of fundamental importance for theoretical and experimental science. In particular, the investigations on bond-breaking and new bond-forming processes triggered by the ionic impact may shed light on the stellar wind interaction with interstellar media, ionic beam irradiations of the living cells, ion-track nanotechnology, radiation hardness analysis of materials, and focused ion beam etching, deposition, and lithography. Due to its vital role in the natural environment, the pyridine molecule has become the subject of both basic and applied research in recent years. Therefore, dissociation of the gas phase pyridine (C5H5N) into neutral excited atomic and molecular fragments following protons (H+) and dihydrogen cations (H2+) impact has been investigated experimentally in the 5-1000 eV energy range. The collision-induced emission spectroscopy has been exploited to detect luminescence in the wavelength range from 190 to 520 nm at the different kinetic energies of both cations. High-resolution optical fragmentation spectra reveal emission bands due to the CH(A2Δ→X2Πr; B2Σ+→X2Πr; C2Σ+→X2Πr) and CN(B2Σ+→X2Σ+) transitions as well as atomic H and C lines. Their spectral line shapes and qualitative band intensities are examined in detail. The analysis shows that the H2+ irradiation enhances pyridine ring fragmentation and creates various fragments more pronounced than H+ cations. The plausible collisional processes and fragmentation pathways leading to the identified products are discussed and compared with the latest results obtained in cation-induced fragmentation of pyridine.

Charge Transfer, Complexes Formation and Furan Fragmentation Induced by Collisions with Low-Energy Helium Cations.

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, 3D1,2,3 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.

Yields and Time-of-Flight Spectra of Neutral High-Rydberg Fragments at the K Edges of the CO2 Molecule.

We have studied the production of neutral fragments in high-Rydberg (HR) states at the C 1s and O 1s edges of the CO2 molecule by performing two kinds of experiments. First, the yields of neutral HR fragments were measured indirectly by ionizing such fragments in a static electric field and by collecting resulting singly charged positive ions as a function of the photon energy. Such measurements reveal not only excitations below the core ionization thresholds but also thresholds for single core-hole and shakeup photoionization. Second, we obtained the mass spectra of neutral HR fragments at selected photon energies by exploiting pulsed field ionization; they show atomic fragments C(HR) and O(HR). We discuss dissociation pathways leading to the production of neutral HR fragments in core excitation and ionization of CO2.

Observation of the Hydrogen Migration in the Cation-Induced Fragmentation of the Pyridine Molecules.

The ability to selectively control chemical reactions related to biology, combustion, and catalysis has recently attracted much attention. In particular, the hydrogen atom relocation may be used to manipulate bond-breaking and new bond-forming processes and may hold promise for far-reaching applications. Thus, the hydrogen atom migration preceding fragmentation of the gas-phase pyridine molecules by the H(+), H2(+), He(+), He(2+), and O(+) impact has been studied experimentally in the energy range of 5-2000 eV using collision-induced luminescence spectroscopy. Formation of the excited NH(A(3)Π) radicals was observed among the atomic and diatomic fragments. The structure of the pyridine molecule is lacking of the NH group, therefore observation of its A(3)Π â†’ X(3)Σ(-) emission bands is an evidence of the hydrogen atom relocation prior to the cation-induced fragmentation. The NH(A(3)Π) emission yields indicate that formation of the NH radicals depends on the type of selected projectile and can be controlled by tuning its velocity. The plausible collisional mechanisms as well as fragmentation channels for NH formation in pyridine are discussed.

Fragmentation of tetrahydrofuran molecules by H(+), C(+), and O(+) collisions at the incident energy range of 25-1000 eV.

We have studied fragmentation processes of the gas-phase tetrahydrofuran (THF) molecules in collisions with the H(+), C(+), and O(+) cations. The collision energies have been varied between 25 and 1000 eV and thus covered a velocity range from 10 to 440 km/s. The following excited neutral fragments of THF have been observed: the atomic hydrogen H(n), n = 4-9, carbon atoms in the 2p3s (1)P1, 2p4p (1)D2, and 2p4p (3)P states and vibrationally and rotationally excited diatomic CH fragments in the A(2)Δ and B(2)Σ(-) states. Fragmentation yields of these excited fragments have been measured as functions of the projectile energy (velocity). Our results show that the fragmentation mechanism depends on the projectile cations and is dominated by electron transfer from tetrahydrofuran molecules to cations. It has been additionally hypothesized that in the C(+)+THF collisions a [C-C4H8O](+) complex is formed prior to dissociation. The possible reaction channels involved in fragmentation of THF under the H(+), C(+), and O(+) cations impact are also discussed.

Hydrogen migration in formation of NH(A³Π) radicals via superexcited states in photodissociation of isoxazole molecules.

Formation of the excited NH(A(3)Π) free radicals in the photodissociation of isoxazole (C3H3NO) molecules has been studied over the 14-22 eV energy range using photon-induced fluorescence spectroscopy. The NH(A(3)Π) is produced through excitation of the isoxazole molecules into higher-lying superexcited states. Observation of the NH radical, which is not a structural unit of the isoxazole molecule, corroborates the hydrogen atom (or proton) migration within the molecule prior to dissociation. The vertical excitation energies of the superexcited states were determined and the dissociation mechanisms of isoxazole are discussed. The density functional and ab initio quantum chemical calculations have been performed to study the mechanism of the NH formation.