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Nitroimidazoles are a class of chemicals with a remarkable broad spectrum of applications from the production of explosives to the use as radiosensitizers in radiotherapy. The understanding of thedynamics of their fragmentation induced by ionizing sources is of fundamental interest. The goal of this work is to theoretically investigate the kinetic competition between the two most important decomposition channels of 2, 4 and 5-Nitroimidazole cations: the NO and NO2 losses. The calculated rate constants of the two processes are in very good agreement with the experimental Photoelectron-Photoion Coincidence (PEPICO) branching ratio. This study solves the intriguing and theoretically unexplained experimental observation that 2-Nitroimidazole, at variance with the other two regio-isomers is a source for only NO at low energies (

The near-edge X-ray absorption fine structure (NEXAFS) spectra of indole, 2,3-dihydro-7-azaindole, and 3-formylindole in the gas phase have been measured at the carbon and nitrogen K-edges. The spectral features have been interpreted based on density functional theory (DFT) calculations within the transition potential (TP) scheme, which is accurate enough for a general description of the measured C 1s NEXAFS spectra as well as for the assignment of the most relevant features. For the nitrogen K-edge, the agreement between experimental data and theoretical spectra calculated with TP-DFT was not quite satisfactory. This discrepancy was mainly attributed to the many-body effects associated with the excitation of the core electron, which are better described using the time-dependent density functional theory (TDDFT) with the range separated hybrid functional CAM-B3LYP. An assignment of the measured N 1s NEXAFS spectral features has been proposed together with a complete description of the observed resonances. Intense transitions from core levels to unoccupied antibonding π* states as well as several transitions with mixed-valence/Rydberg or pure Rydberg character have been observed in the C and N K-edge spectra of all investigated indoles.

Methanol is one of the most abundant and ubiquitous molecules in the space. Its chemistry is fundamental to understand the molecular growing from prebiotic molecules, ions and radicals. In this work the reaction of labelled methanol CD3OH•+ radical cation, produced with different internal energies by monochromatic synchrotron radiation, with neutral CD3OH was studied. The dynamics of the main reaction channels were investigated by theoretical calculations. The results show how these processes can be considered suitable pathways for the formation of fundamental species as CH3O(H)H+, CH3O•, •CH2OH, CH2O which are potential precursors to prebiotic molecules.

Superhydrogenated polycyclic aromatic hydrocarbons (PAHs) have been suggested to catalyze the formation of H2 in certain regions of space, but it remains unclear under which circumstances this mechanism is viable given the reduced carbon backbone stability of superhydrogenated PAHs. We report a laboratory study on the stability of the smallest pericondensed PAH, pyrene (C16H10+N , with N = 4, 6, and 16 additional H atoms), against photodestruction by single vacuum ultraviolet photons using the photoelectron–photoion coincidence technique. For N = 4, we observe a protective effect of hydrogenation against the loss of native hydrogens, in the form of an increase in the appearance energies of the and C16H8 + daughter ions compared to those reported for pristine pyrene (C16H10). No such effect is seen for N = 6 or 16, where the weakening effect of replacing aromatic bonds with aliphatic ones outweighs the buffering effect of the additional hydrogen atoms. The onset of fragmentation occurs at similar internal energies for N = 4 and 6, but is significantly lower for N = 16. In all three cases, H-loss and C m H n -loss (m ≥ 1, carbon backbone fragmentation) channels open at approximately the same energy. The branching fractions of the primary channels favor H-loss for N = 4, C m H n -loss for N = 16, and are roughly equal for the intermediate N = 6. We conclude that superhydrogenated pyrene is probably too small to support catalytic H2-formation, while trends in the current and previously reported data suggest that larger PAHs may serve as catalysts up to a certain level of hydrogenation.

A combined experimental and theoretical study shows how the interaction of VUV radiation with cyclo-(alanine-alanine), one of the 2,5-diketopiperazines (DKPs), produces reactive oxazolidinone intermediates. The theoretical simulations reveal that the interaction of these intermediates with other neutral and charged fragments, released in the molecular decomposition, leads either to the reconstruction of the cyclic dipeptide or to the formation of longer linear peptide chains. These results may explain how DKPs could have, on one hand, survived hostile chemical environments and, on the other, provided the seed for amino acid polymerization. Shedding light on the mechanisms of production of such prebiotic building blocks is of paramount importance to understanding the abiotic synthesis of relevant biologically active compounds, This article is based upon work from COST action CA18212 - Molecular Dynamics in the GAS phase (MD-GAS), supported by COST (European Cooperation in Science and Technology). The authors acknowledge the generous allocation of computer time at the Centro de Computación Cientıfí ca at the Universidad Autonoma de Madrid (CCC-UAM). This work ́ was partially supported by MICINN (Spanish Ministry of Science and Innovation) project PID2019-110091GB-I00, the “Marıa de Maeztu ́ ” (CEX2018-000805-M) Program for Centers of Excellence in R&D, MAECI Italy-Sweden project “Novel molecular tools for the exploration of the nanoworld”, and PRIN 20173B72NB project “Predicting and controlling the fate of biomolecules driven by extreme-ultraviolet radiation”. D.B.-L. acknowledges the FPI grant associated with MICINN project CTQ2016-76061-P. H.Z. acknowledges the Swedish Research Council for the individual project grant with contract no. 2020- 03437

The Auger spectrum of argon in the kinetic energy region (135-235 eV) has been measured using a non-monochromatic electron beam (incident energy from 313 to 2019 eV) at two ejection angles of 60 degrees and 90 degrees with a high resolution electrostatic analyzer. The electron impact energies of 313 and 323 eV have been used in order to disentangle the contribution of the ionization and decay of the 2s state. The systematic analysis of the measured spectra shows the dominance of the Coster-Kronig transitions from the 2s ionization in the energy region 135-159 eV and 208-235 eV, while the Auger transitions from the 2p ionization are dominant in the energy region 160-208 eV. The high resolution of the present work led to the observation of a certain number of new features in two energy regions 135-159 and 208-235 eV, respectively. Recent literature data on the cascade Auger processes and threshold formation of Ar2+ satellite states allow the assignment of some of them, while other have been left without assignments. The influence of the PCI effect on the line-shape, width and energy position of the features in the kinetic energy region 200-208 eV has been also investigated and the PCI shift versus excess energy above threshold compared with previous data and theoretical predictions.

Dihalomethanes XCH2Y (X and Y = F, Cl, Br, and I) are a class of compounds involved in several processes leading to the release of halogen atoms, ozone consumption, and aerosol particle formation. Neutral dihalomethanes have been largely studied, but chemical physics properties and processes involving their radical ions, like the pathways of their decomposition, have not been completely investigated. In this work the photodissociation dynamics of the ClCH2I molecule has been explored in the photon energy range 9-21 eV using both VUV rare gas discharge lamps and synchrotron radiation. The experiments show that, among the different fragment ions, CH2I+ and CH2Cl+, which correspond to the Cl- and I-losses, respectively, play a dominant role. The experimental ionization energy of ClCH2I and the appearance energies of the CH2I+ and CH2Cl+ ions are in agreement with the theoretical results obtained at the MP2/CCSD(T) level of theory. Computational investigations have been also performed to study the isomerization of geminal [ClCH2I]o+ into the iso-chloroiodomethane isomers: [CH2I-Cl]o+ and [CH2Cl-I]o+.

Synopsis The electronic structure and the fragmentation dynamics of a series of isolated cyclic-dipeptides (cyclo-Ala-Ala; cyclo-Gly-Ala; cyclo-Gly-Gly) have been studied by mass spectrometry, photoemission and photoelectron-photoion coincidence spectroscopy.

The valence and core-level photoelectron spectra of gaseous indole, 2,3-dihydro-7-azaindole, and 3-formylindole have been investigated using VUV and soft X-ray radiation supported by both an ab initio electron propagator and density functional theory calculations. Three methods were used to calculate the outer valence band photoemission spectra: outer valence Green function, partial third order, and renormalized partial third order. While all gave an acceptable description of the valence spectra, the last method yielded very accurate agreement, especially for indole and 3-formylindole. The carbon, nitrogen, and oxygen is core-level spectra of these heterocycles were measured and assigned. The double ionization appearance potential for indole has been determined to be 21.8 +/- 0.2 eV by C is and N is Auger photoelectron spectroscopy. Theoretical analysis identifies the doubly ionized states as a band consisting of two overlapping singlet states and one triplet state with dominant configurations corresponding to holes in the two uppermost molecular orbitals. One of the singlet states and the triplet state can be described as consisting largely of a single configuration, but other doubly ionized states are heavily mixed by configuration interactions. This work provides full assignment of the relative binding energies of the core level features and an analysis of the electronic structure of substituted indoles in comparison with the parent indole.

The Kr M4,5-NN Auger transitions are studied in the kinetic energy region 24 - 59 eV by using non-monochromatic electron beam and a high resolution electrostatic analyzer. Among the sixty four features observed, fifty five are assigned, while nine stay unassigned. The post-collision interaction (PCI) effects in the M5-N1N1(1S0) and M5-N2,3N2,3(1S0) Auger peaks are studied as a function of electron incident energy approaching the M5 edge (95.04 eV). The PCI shifts are found to be well represented by an exponential function of the excess energy with exponents β = (-0.99±0.05 and -3.08±0.05) for the N2,3N2,3(1S0) and N1N1(1S0) peaks, respectively. The M2,3-M4,5N Coster-Kronig transitions are studied in kinetic energy region 65 - 110 eV and at incident energies from 120 to 2019 eV. Owing to a high resolution twelve well resolved satellites in the region bellow 90 eV are observed, while in the region 90 - 110 eV two broad features are assigned to the M2,3-M4,5N2,3 C-K peaks with intensity ratio (M3/M2 = 2.37) are observed. Comparison is made with available data from literature.

Hot-carriers, that is, charge carriers with an effective temperature higher than that of the lattice, may contribute to the high power conversion efficiency (PCE) shown by perovskite-based solar cells (PSCs), which are now competitive with silicon solar cells. Hot-carriers lose their excess energy in very short times, typically in a few picoseconds after excitation. For this reason, the carrier dynamics occurring on this time scale are extremely important in determining the participation of hot-carriers in the photovoltaic process. However, the stability of PSCs over time still remains an issue that calls for a solution. In this work, we demonstrate that the insertion of graphene flakes into the mesoscopic TiO2 scaffold leads to stable values of carrier temperature. In PSCs aged over 1 week, we indeed observe that in the graphene-free perovskite cells the carrier temperature decreases by about 500 K from 1800 to 1300 K, while the graphene-containing cell shows a reduction of less than 200 K after the same aging time delay. The stability of the carrier temperature reflects the stability of the perovskite nanocrystals embedded in the mesoporous graphene-TiO2 layer. Our results, based on femtosecond transient absorption measurements, show that the insertion of graphene can be beneficial for the design of stable PSCs with the aim of exploiting the hot-carrier contribution to the PCE of the PSCs.

Hydrogen migration in the glycine cation has been investigated using a combination of a short train of attosecond extreme ultraviolet pulses with few-optical-cycle near-infrared pulses. The yield of the photofragments produced has been measured as a function of pump–probe delay. These time-dependent measurements reveal the presence of a hydrogen migration process occurring in 48 fs. Previous mass spectrometric experiments and theoretical calculations have allowed us to identify the conformations and cation states involved in the process induced by the broad band extreme ultraviolet radiation.

The fragmentation of glycine (NH2CH2COOH) has been studied by photoelectron-photoion coincidence, PEPICO, experiments at 60 eV photon energy. Glycine practically fragments at the ionization threshold, with the charge being on the H2NCH2+ moiety, due to ejection of an electron from the nitrogen lone pair of the highest occupied molecular orbital. To observe the formation of the complementary cation COOH+ further energy is needed. The flexibility with respect to rotation about the C-C, C-N and C-O bonds makes glycine exist in the gas phase in several conformers of both Cs and C1 point group symmetry in the neutral as well as ion states. The ionization can lead to stabilization of some conformations, rearrangements and, last but not least, H migration between the two moieties. The results of these experiments prove the sensitivity of PEPICO to pin point all these processes.

Synchrotron radiation and synchrotron based spectroscopic techniques have found important applications in the study of isolated molecular species of biological interest. In this paper, some examples of spectroscopic and dynamic studies of amino acids and small peptides, nucleobases and pharmaceuticals are reviewed. Opportunities offered by the advent of new radiation sources combined with novel methods for the production of beams of these molecules are also discussed.

Nitromidazoles are relevant compounds of multidisciplinary interest, and knowledge of their physical chemical parameters as well as their decomposition under photon irradiation is needed. Here we report an experimental and theoretical study of the mechanisms of VUV photo fragmentation of 2- and 4(5)-nitromidazoles, compounds used as radiosensitizers in conjunction with radiotherapy as well as high-energy density materials. Photoelectron photoion coincidence experiments, measurements of the appearance energies of the most important ionic fragments, density functional theory, and single-point coupled cluster calculations have been used to provide an overall insight into the energetics and structure of the different ionic/neutral products of the fragmentation processes. The results show that these compounds can be an efficient source of relevant CO, HCN, NO, and NO2 molecules and produce ions of particular astrophysical interest, like the isomers of azirinyl cation (m/z 40), predicted to exist in the interstellar medium, and protonated hydrogen cyanide (m/z 28).

The X-ray absorption spectra (XAS) of Ar-2 and ArNe dimers and small Ar clusters in the L-2,L-3 region (244-252 eV) of the Ar atom have been recorded using synchrotron light and a combination of coincidence methods and kinetic energy discrimination of energetic ions. The absorption peaks in the spectra of the dimers and clusters were found to be shifted and broadened relative to the peaks in the spectrum of the Ar atom. In order to unambiguously relate these chemical shifts to the electronic structure of the core excited states in dimers, we performed ab initio calculations of the XAS spectra. Implications of the results for the use of XAS as a structure determination method in large rare gas clusters are discussed.

[object Object]The fragmentation of the isolated 5-bromouracil (5BrU) molecule and pure and nano-hydrated 5BrU clusters induced by low energy C-12(4+) ions has been studied. A comparison indicates that the environment, on the one hand, protects the system against the complete break-up into small fragments, but, on the other hand, triggers 'new' pathways for fragmentation, for example the loss of the OH group. The most striking result is the observation of several series of hydrated fragments in the hydrated cluster case, with water molecules bound to hydrophilic sites of 5BrU. This highlights the strong interaction between 5BrU and water molecules and the blocking of specific fragmentation pathways, such as the loss of the BrC2H group for example.

Synopsis This work relies on complementary theoretical and experimental studies of the processes induced by ion-furan collisions. Results of the Molecular Dynamics simulations and exploration of the energy profiles combined with coincidence mass spectrometry provide complete picture of the fragmentation of furan dication.

The electronic structures of nicotine, nicotinic acid and nicotinamide have been studied by valence photoemission spectroscopy (PES), core X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorp- tion fine structure (NEXAFS) and interpreted with the aid of quantum chemical calculations. Nicotinamide and nicotinic acid are closely related and show correspondingly similar spectral features, while nicotine is both struc- turally and spectroscopically diverse

This is the accepted manuscript of the paper""position" does matter : the photofragmentation of the nitroimidazole isomers" published as final paper in Journal of Physics: Conference Series 2017, 875, 032007

A combined experimental and theoretical approach has been used to disentangle the fundamental mechanisms of the fragmentation of the three isomers of nitroimidazole induced by vacuum ultra-violet (VUV) radiation, namely, 4-, 5-, and 2-nitroimidazole. The results of mass spectrometry as well as photoelectron-photoion coincidence spectroscopy display striking differences in the radiation-induced decomposition of the different nitroimidazole radical cations. Based on density functional theory (DFT) calculations, a model is proposed which fully explains such differences, and reveals the subtle fragmentation mechanisms leading to the release of neutral species like NO, CO, and HCN. Such species have a profound impact in biological media and may play a fundamental role in radiosensitising mechanisms during radiotherapy.

High resolution ejected electron spectroscopy has been used to investigate a large number of Ar autoionizing states producing ejected electrons in the energy range from 6 to 26 eV at impact electron energies of 505 and 2018 eV and ejection angles of 40°, 90° and 130°. The full energy range has been divided into three regions which were analyzed separately. In the first one (6–9 eV) the obtained features are identified as the decay of the Ar2+(1D) at 45.11 eV. In the second one (9–14 eV) all features are identified as due to the decay of excited states formed by the excitation of 3s electrons to ns, np and nd subshells. The most prominent features are those arising from the excitation of 3s to nd(3,1D). In this series the 3s3p 63d(1D) state with FWHM of 0.040 eV is used as the calibration point for all measured spectra. In the third energy region (14–26 eV) a large number of features is observed. Most of them are identified as the decay of excited states of the type 3s3p 5 nl and 3s 23p 4 nl n′l′.

International audience; The fragmentation of uracil molecules and pure and nano-hydrated uracil clusters by 12C4+ ion impact is investigated. This work focuses on the fragmentation behavior of complex systems and the effect of the environment. On the one hand, it is found that the environment in the form of surrounding uracil or water molecules has a significant influence on the fragmentation dynamics, providing an overall ‘protective’ effect, while on the other hand we observe the opening of specific fragmentation channels. In particular, we report on the first observation of a series of hydrated fragments. This indicates a strong interaction between uracil and water molecules, holding the water clusters bound to the observed molecular fragments.

The fragmentation of a polyatomic molecular dication has been investigated by means of a Monte Carlo simulation which can take into account realistic experimental conditions. The simulation applied to the three body process CH 4 2+ → CH 2 + + H + + H shows that the low angular acceptance, consequence of the low extraction field, does not prevent the distinction between the initial charge separation and the synchronous concerted decay mechanisms, which lead to the same final state. The comparison of the results with recent experiments [1] confirms that an initial charge separation with a following loss of a hydrogen atom describes better the experimental observations.

The inner shell ionization of pyrimidine and some halogenated pyrimidines has been investigated experimentally by X-ray photoemission spectroscopy (XPS) and theoretically by density functional theory (DFT) methods. The selected targets 5-Br-pyrimidine, 2-Br-pyrimidine, 2-Cl-pyrimidine, and 5-Br-2-Cl-pyrimidine allowed the study of the effect of the functionalization of the pyrimidine ring by different halogen atoms bound to the same molecular site, or by the same halogen atom bound to different molecular sites. The theoretical investigation of the inductive and resonance effects in the C(1s) ionization confirms the soundness of the resonance model for a qualitative description of the properties of an aromatic system. Moreover, the combination of the experimental results and the theoretical analysis provides a detailed description of the effects of the halogen atom on the screening of a C(1s) hole in the aromatic pyrimidine ring.

The electronic structures of pyrimidine and a selection of its halogen-substituted derivatives have been investigated using ultraviolet photoelectron spectroscopy and ab initio quantum chemical methods. Assignments are proposed for all of the features in the PES spectra by comparison with the vertical ionization energies of the molecular orbitals calculated using the partial third-order quasiparticle approximation as applied to electron propagator theory and a corrected density functional method based on the B3LYP functional. The shifts of the outermost five molecular orbitals of the pyrimidine ring structure in the halogen-substituted derivatives with respect to the binding energies of the equivalent orbitals in the parent pyrimidine molecule are discussed as a function of the identity and ring position of the halogen atom.

The conformational landscape of (S)-1-(4-chlorophenyl)ethanol, its monohydrated complex, and its diastereomeric adducts with R- and S-butan-2-ol, have been investigated by resonant two-photon ionization (R2PI) spectroscopy coupled with time-of-flight mass spectrometry. Theoretical calculations at the D-B3LYP/6-31++G** level of theory have been performed to assist in the interpretation of the spectra and in the assignment of the structures. The R2PI spectra and the predicted structures have been compared with those obtained on the analogous non-halogenated and fluorinated systems, i.e., (R)-1-phenylethanol and (S)-1-(4-fluorophenyl)ethanol, respectively. It appears that the presence of chlorine atom in the para position of the aromatic ring does not influence the overall geometry of bare molecule and its complexes with respect to the non-halogenated analogous systems. Anyway, it affects the electron density in the pi system, and in turn the strength of OH···pi and CH···pi interactions. A spectral chiral discrimination is evident from the R2PI spectra of the diastereomeric adducts of (S)-1-(4-chlorophenyl)ethanol with the two enantiomers of butan-2-ol.

The fragmentation of the CH 4 2+ dication has been studied in an electron impact experiment by Auger electron-ion and Auger electron-ion–ion coincidence measurements. Different states of the dications have been selected by changing the kinetic energy of the Auger electrons. Particular attention has been paid to the production of the CH 2 + and CH 3 + ions whose Kinetic Energy Release (KER) distributions and dissociation channels have been determined. Moreover, for the first time in an electron impact experiment, the C 2+ ion fragment has been identified.

The inner-shell excitation and decay of the CO molecule have been studied in electron impact experiments. The dipole-forbidden transition (1s sigma(c))(-1)(2p pi) (3)Pi has been characterized by angular resolved electron energy loss spectroscopy and its decay via the measurement of resonant Auger spectra. The contribution of the (1s sigma(c))(-1)(2p pi)(3)Pi state to the CO resonant Auger spectrum in the region of the "spectator transitions" has been isolated and the population of CO+ quartet final states has been observed. (C) 2006 Elsevier Ltd. All rights reserved.

Ejected electron spectroscopy has been used to study singly and doubly excited states of neon at constant incident electron energies between 505 and 2018 eV and ejection angles from 10° to 130° with high resolution in ejected energy range from 12 to 46 eV. The full ejected electron energy range has been studied at two extreme incidence energies and three ejected angles, namely 40°, 90° and 130°. The low energy region (12 to 21.5 eV) has been investigated at 505 eV over the full angular range and at 90° at six incident energies from 505 to 2018 eV. The features in the ejected electron spectra have been attributed to the autoionisation of Ne+ (2s2p 6 nl) excited states and Ne (2s2p 5 nl n′l′ and 2s 22p 4 nl n′l′) double excited autionising states. Lower energy ejected electrons arise from simultaneous excitation of s and p electrons above the second ionisation potential (62.53 eV) while higher energy ejected electrons are coming from singly and doubly excited states. The high resolution and high sensitivity allowed us to see separated singlet from triplet states at high incident energies. Comparison with previous works gives a good agreement in energy positions of measured features. At the highest ejected electron energies only the features coming from double excitation are present, but with very low intensities in the spectra due to the small cross sections and high background. New resonances are found whose classification needs new experimental and theoretical investigations.

In this work we have studied the 4d photoexcitation of atomic cesium vapor at high resolution in the energy range 75–90 eV. Below threshold, the two series of the 4d 10 6s → 4d 9 6s6p 3,1 P discrete transitions are observed to dominate the measured ion-yield spectra. The high photon energy resolution allowed us to selectively excite specific resonances. In this way the decay of the different excited states lying close to each other could be followed with a minimum of interference from overlapping transitions. Here we present the resonant Auger spectra recorded at the lowest energy 4d excited states and a preliminary analysis based on previous experimental and theoretical results.

The threshold photoelectron spectrum of benzene has been recorded up to 26.5 eV photon energy under high-resolution conditions using synchrotron radiation and employing the penetrating-field threshold electron collection method. By means of a direct comparative study with a recent HeI photoelectron spectrum of benzene of equally high resolution, numerous autoionization effects are observed in the formation of the ionic band systems of benzene in the outer valence ionization region in the threshold photoelectron spectrum. The Rydberg states responsible for these effects are identified. Autoionization does not appear to play a role in the formation of the two lowest-energy, inner-valence bands of C6H6+.Key words: threshold photoelectron spectroscopy, photoelectron spectroscopy, benzene, ionization, autoionization, Rydberg states.

Recent work devoted to the study of photo-double-ionization of atoms is reviewed. This process is of much current interest because it is completely dominated by electron–electron correlations. In particular, experimental studies based on the techniques of low energy electron spectroscopy are described in the region near the double ionization threshold, together with ( γ , 2e) coincidence experiments performed above this threshold. By using selected examples from non-coincidence and coincidence experiments the various kinds of dynamic and spectroscopic information that can be obtained are illustrated. Recent results, mainly in the rare gases, are described and their interpretation discussed. Future perspectives are considered.

The chemical physics of halomethanes is an important and challenging topic in several areas of chemistry in particular in the chemistry of the atmosphere. Among the class of halomethanes, the diiodomethane molecule has attracted some interest in the last years, but despite this, the information on its radical cation [CH2I2](⋅+) is still limited. In this work, we measured and calculated the appearance energy (AE) of the ionic fragments I2(⋅+) and CH2(⋅+) and correlated the different fragmentation channels to the electronic states of the cation via photoelectron-photoion coincidence (PEPICO) experiments. In the case of the CH2/I2(⋅+) channel, the experimentally determined AE is in excellent agreement with the adiabatic theoretical value while a discrepancy is observed for the CH2(⋅+)/I2 channel. This discrepancy can be understood accounting for a fragmentation involving the formation of two I atoms (CH2(⋅+)/2I channel), which, as explained by time dependent density functional theory (TD-DFT) calculations, occurs when [CH2I2](⋅+) excited states are involved.

The time resolved photoionization of C 1s in uracil following excitation of the neutral molecule by 260 nm pulses has been studied at LCLS.

We present a combined experimental and theoretical study of the ionisation and fragmentation of the nucleoside thymidine in the gas phase. Two sources of ionisation/excitation are used, namely UV photons and low-energy multiply charged ions, associated with coincidences measurements, respectively photoelec- tron/photofragment (PEPICO) and fragment/fragment. Coupling these experiments with quantum chemistry calculations, we obtain a complete picture of the fragmentation dynamics, in particular the charge and energy transfers within the molecular edifice.

International audience; The fragmentation of the 2Br-pyrimidine molecule following direct valence photoionization or inner shell excitation has been studied by electron–ion coincidence experiments. 2Br-pyrimidine has been chosen as a model for the class of pyrimidinic building blocks of three nucleic acids and several radiosensitizers. It is known that the site- and state-localization of energy deposition, typical of inner shell excitation, results in the enhancement of the total ion yield as well as in changes in the relative intensity of the different fragmentation channels. Here we address the question of the origin of this selective fragmentation by using electron–ion coincidence techniques. The results show that the fragmentation is strongly selective in the final singly charged ion state, independently of the process that leads to the population of that state, and the dominant fragmentation patterns correlate with the nearest appearance potential.

Collective excitation in polycyclic aromatic hydrocarbon molecule is studied in collision experiments with intermediate velocity (50-180 keV) proton and FUV (15-40 eV) photon energy. In proton impact experiments a clear comparison between pure ionization and capture ionization (or pure capture) process is done on the basis of ionization, evaporation, fragmentation process as a function of impact energy. Two mechanisms: large impact parameter collective excitation mode and closer encounters with higher amount of electronic energy loss leading to fragmentation were observed in proton collision process. The photon impact results were used to understand the origin of evaporation processes.

Diiodomethane is an important halocarbon responsible for several atmospheric processes like ozone depletion and aerosol particle formation. Despite this, the thermochemical data and a detailed analysis of the pathways for the decomposition of this halomethane and its molecular ion [CH2I2](•+) are scarce. In this paper an investigation of the photodissociation dynamics of the CH2I2 molecule focused on the I-loss channel by the photoelectron-photoion coincidence (PEPICO) technique and computational methods is reported. The experimental results show that upon VUV irradiation the dissociation of the lower electronic ionic states of diiodomethane leads only to the CH2I(+) ion and the I atom. The theoretical calculations point out that isomerization of [CH2I2](•+) into iso-diiodomethane [CH2I-I](•+) may play an important role in the emission of iodine atom as compared to direct C-I bond breaking.

The coplanar (e, 3e) relative cross sections for double ionization of argon have been measured at an electron impact energy of E0 = 561.4 eV and under equal energy sharing among the two 'ejected' electrons, Eb = Ec = 9 eV. The scattering angle is fixed to ?a = 1.5?, corresponding to a momentum transfer K = 0.4 au to the target. The experimental results have been compared with calculations in the first Born approximation, which include only first-order processes in the target?projectile interaction. The comparison shows severe deviations between the experimental and theoretical results. These deviations are much larger than the ones previously observed in helium under comparable kinematics. To fill this gap between theory and experiment, a decisive improvement in the theory is needed. This can be achieved by improving the first-order calculations and by including higher-order processes such as the two-step mechanism, or even new mechanisms, for instance the simultaneous ejection of the pair of target electrons.

In the present work we have studied the photoinduced ion chemistry of the 2Cl-pyrimidine molecule in the energy region 9-14 eV. The theoretical gas phase enthalpies of formation of the main fragments calculated using the G3B3 and G2 ab initio methods are compared to the experimental values, derived by the measured appearance energy of the fragments. This approach provides new insights into both the geometric structure of the ionic fragments and the basic mechanisms governing the molecular fragmentation.

Inner and outer valence photoelectron spectra (PES) of pyrene and fluorene, two members of the polycyclic aromatic hydrocarbon (PAH) family, were recorded with a high-resolution synchrotron photoelectron spectrometer. Relative photoelectron emission cross sections were measured at photon energies between 15 and 40 eV. Several bands observed in the experimental PES were assigned with the help of OVGF/cc-pVDZ calculations. The first ionization potentials were estimated to be 7.436 ± 0.015 and 7.944 ± 0.055 eV for pyrene and fluorene, respectively. Photoelectron emission cross sections show a clear difference in trend for inner (?-dominated) and outer (?-dominated) bands. Contrary to the expectation from the trend observed in benzene, the inner bands significantly dominate in the photon energy region from 15 to 27 eV and then are found to contribute uniformly. A pronounced peak in the cross sections is observed at a photon energy of approximately 17 eV for both molecules (irrespective of the difference in symmetry and structure), particularly for the inner valence bands. The feature is observed to be independent of the details of the molecular orbital associated with the outgoing electron. These observations are correlated to a collective excitation in the far-ultraviolet region. © 2014 American Chemical Society.

Fluorescence decay of the 2s2p(6)np (1)P(o) excited states of neon has been observed directly for the first time. This process has also been observed indirectly by threshold photoelectron spectroscopy and in electron/photon coincidences. The measurements have allowed this weak decay channel to be characterized and branching ratios derived. The fluorescence excitation spectrum is well described by a simple Rydberg model that highlights the interplay and competition between the decay channels of autoionization and fluorescence.

Threshold photoelectron-photoelectron coincidence experiments have been used to study the dissociative double ionisation of O 2 . The results show that the main dissociative process involves the formation of neutral excited oxygen atoms.

The ${L}_{1}\ensuremath{-}{L}_{2,3}M$ Coster-Kronig spectrum of argon has been measured by using photon excitation. The intensity ratio of $0.30\ifmmode\pm\else\textpm\fi{}0.02$ between the ${L}_{1}\ensuremath{-}{L}_{2,3}{M}_{1}$ main lines and the ${L}_{1}\ensuremath{-}{L}_{2,3}{M}_{2,3}$ lines is extracted from experiment. The experimental results for the ratio and partial decay rates are compared with present and previous theoretical estimates.

Angle-resolved ${M}_{4,5}{N}_{4,5}{N}_{4,5}$ Auger spectra of xenon have been measured near the Xe $3d$ threshold by using synchrotron radiation excitation. The angular anisotropy parameters extracted from the experimental data generally agree with the recent theoretical results based on multiconfiguration Dirac-Fock calculations. The angle-resolved measurements have also been employed in order to study the character of the resonance structures below the ${M}_{4}$ threshold.