Few-femtosecond electron transfer dynamics in photoionized donor-π-acceptor molecules.

The exposure of molecules to attosecond extreme-ultraviolet (XUV) pulses offers a unique opportunity to study the early stages of coupled electron-nuclear dynamics in which the role played by the different degrees of freedom is beyond standard chemical intuition. We investigate, both experimentally and theoretically, the first steps of charge-transfer processes initiated by prompt ionization in prototype donor-π-acceptor molecules, namely nitroanilines. Time-resolved measurement of this process is performed by combining attosecond XUV-pump/few-femtosecond infrared-probe spectroscopy with advanced many-body quantum chemistry calculations.

Fragmentation dynamics of the doubly charged aniline: the source of kinetically excited CH ions.

The goals of this work are to attempt to decipher if an aniline dication can isomerize to a picoline dication in a given astrochemical environment and if the dissociation of such dications could be a source of kinetically hot fragment ions, some of which could be of significance in the interstellar medium. Toward this purpose, the VUV-induced dication dissociation was investigated experimentally using ion-ion coincidence and computationally by optimizing various pathways. Contrary to previous reports, we show here that the dication of aniline is structurally too weak to retain its ring structure while following the dissociation pathways.

Coincidence measurements of photodouble ionization of benzene and thiophene.

Photodouble ionization (PDI) triple-differential cross sections (TDCSs) of benzene and thiophene have been measured in electron-electron coincidence experiments under 10-10 eV and 20-20 eV equal energy sharing conditions. A multi-Gaussian fit method has been employed to characterize the TDCSs. The trends and features observed for benzene and thiophene do highlight differences with helium most likely from molecular PDI contributions to the TDCS.

In search of universalities in the dissociative photoionization of PANHs via isomerizations.

In search of the cause behind the similarities often seen in the fragmentation of PANHs, vacuum ultraviolet (VUV) photodissociation of two pairs of isomers quinoline-isoquinoline and 2-naphthylamine-3-methyl-quinoline are studied using the velocity map imaging technique. The internal energy dependence of all primary fragmentation channels is obtained for all four target molecules. The decay dynamics of the four molecules is studied by comparing their various experimental signatures.

HO˙ and OH reactivity furan: experimental low energy absolute cross sections for modeling radiation damage.

Radiotherapy is one of the most widespread and efficient strategies to fight malignant tumors. Despite its broad application, the mechanisms of radiation-DNA interaction are still under investigation. Theoretical models to predict the effects of a particular delivered dose are still in their infancy due to the difficulty of simulating a real cell environment, as well as the inclusion of a large variety of secondary processes.

Autoionization from the plasmon resonance in isolated 1-cyanonaphthalene.

Polycyclic aromatic hydrocarbons have widely been conjectured to be ubiquitous in space, as supported by the recent discovery of two isomers of cyanonaphthalene, indene, and 2-cyanoindene in the Taurus molecular cloud-1 using radioastronomy. Here, the photoionization dynamics of 1-cyanonaphthalene (1-CNN) are investigated using synchrotron radiation over the hν = 9.0-19.

Photofragmentation specificity of photoionized cyclic amino acids (diketopiperazines) as precursors of peptide building blocks.

The photoionisation and photofragmentation of the two cyclic dipetides cyclo(alanyl-glycine) cGA and cyclo(glycyl-glycine) cGG, have been studied combining experiments and simulations. State selected fragments from the ionized molecules are detected using photo-electron photo-ion coincidence (PEPICO) measurements and specific fragmentation paths are identified and characterized the use of ion-neutral coincidence maps. The simulations, performed using Quantum Chemistry methods, allow us to infer the fragmentation mechanisms of the ionized and excited molecules.

A study of the valence photoelectron spectrum of uracil and mixed water-uracil clusters.

The valence ionization of uracil and mixed water-uracil clusters has been studied experimentally and by ab initio calculations. In both measurements, the spectrum onset shows a red shift with respect to the uracil molecule, with the mixed cluster characterized by peculiar features unexplained by the sum of independent contributions of the water or uracil aggregation. To interpret and assign all the contributions, we performed a series of multi-level calculations, starting from an exploration of several cluster structures using automated conformer-search algorithms based on a tight-binding approach.

Electron and ion spectroscopy of azobenzene in the valence and core shells.

Azobenzene is a prototype and a building block of a class of molecules of extreme technological interest as molecular photo-switches. We present a joint experimental and theoretical study of its response to irradiation with light across the UV to x-ray spectrum. The study of valence and inner shell photo-ionization and excitation processes combined with measurement of valence photoelectron-photoion coincidence and mass spectra across the core thresholds provides a detailed insight into the site- and state-selected photo-induced processes.

Photoelectron-photoion(s) coincidence studies of molecules of biological interest.

Photoelectron-photoion(s) coincidence, PEPICO, experiments with synchrotron radiation have become one of the most powerful tools to investigate dissociative photoionization thanks to their selectivity. In this paper their application to the study of molecular species of biological interest in the gas phase is reviewed. Some applications of PEPICO to the study of potential radiosensitizers, amino acids and small peptides and opportunities offered by the advent of novel methods for the production of beams of these molecules are discussed.

Photodissociation of quinoline cation: Mapping the potential energy surface.

A detailed exploration of the potential energy surface of quinoline cation (CHN) is carried out to extend the present understanding of its fragmentation mechanisms. Density functional theory calculations have been performed to explore new fragmentation schemes, giving special attention to previously unexplored pathways, such as isomerization and elimination of HNC. The isomerization mechanisms producing five- to seven-membered ring intermediates are described and are found to be a dominant channel both energetically and kinetically.

Comprehensive survey of dissociative photoionization of quinoline by PEPICO experiments.

Dissociative photoionization of quinoline induced by vacuum ultraviolet radiation is investigated using photoelectron-photoion coincidence spectroscopy. Branching ratios of all the detectable fragment ions are measured as a function of internal energy ranging from 2 to 30 eV. A specific generation hierarchy is observed in the breakdown curves of a set of dissociation channels.

Ion Chemistry of Carbon Dioxide in Nonthermal Reaction with Molecular Hydrogen.

The exothermic hydrogen transfer from H to CO leading to H and HCO is investigated in a combined experimental and theoretical work. The experimental mass/charge ratios of the ionic product (HCO) and the ionic reactant (CO) are recorded as a function of the photoionization energy of the synchrotron radiation. Theoretical density functional calculations and variational transition state theory are employed and adapted to analyze the energetic and the kinetics of the reaction, which turns out to be barrierless and with nonthermal rate coefficients controlled by nonstatistical processes.

Insights into the Thermally Activated Cyclization Mechanism in a Linear Phenylalanine-Alanine Dipeptide.

Dipeptides, the prototype peptides, exist in both linear (-) and cyclo (-) structures. Since the first mass spectrometry experiments, it has been observed that some -structures may turn into the cyclo ones, likely via a temperature-induced process. In this work, combining several different experimental techniques (mass spectrometry, infrared and Raman spectroscopy, and thermogravimetric analysis) with tight-binding and ab initio simulations, we provide evidence that, in the case of l-phenylalanyl-l-alanine, an irreversible cyclization mechanism, catalyzed by water and driven by temperature, occurs in the condensed phase.

Electron and ion spectroscopy of the cyclo-alanine-alanine dipeptide.

The VUV photoionisation and photofragmentation of cyclo-alanine-alanine (cAA) has been studied in a joint experimental and theoretical work. The photoelectron spectrum and the photoelectron-photoion coincidence (PEPICO) measurements, which enable control of the energy being deposited, combined with quantum chemistry calculations, provide direct insight into the cAA molecular stability after photoionisation. The analysis of the ion-neutral coincidence experiments with the molecular dynamics simulations and the exploration of the potential energy surface allows a complete identification of the fragmentation pathways.

Fabrication of a New, Low-Cost, and Environment-Friendly Laccase-Based Biosensor by Electrospray Immobilization with Unprecedented Reuse and Storage Performances.

The fabrication of enzyme-based biosensors has received much attention for their selectivity and sensitivity. In particular, laccase-based biosensors have attracted a lot of interest for their capacity to detect highly toxic molecules in the environment, becoming essential tools in the fields of white biotechnology and green chemistry. The manufacturing of a new, metal-free, laccase-based biosensor with unprecedented reuse and storage capabilities has been achieved in this work through the application of the electrospray deposition (ESD) methodology as the enzyme immobilization technique.

A systematic study of the valence electronic structure of cyclo(Gly-Phe), cyclo(Trp-Tyr) and cyclo(Trp-Trp) dipeptides in the gas phase.

The electronic energy levels of cyclo(glycine-phenylalanine), cyclo(tryptophan-tyrosine) and cyclo(tryptophan-tryptophan) dipeptides are investigated with a joint experimental and theoretical approach. Experimentally, valence photoelectron spectra in the gas phase are measured using VUV radiation. Theoretically, we first obtain low-energy conformers through an automated conformer-rotamer ensemble sampling scheme based on tight-binding simulations.

Ionization of 2- and 4(5)-Nitroimidazoles Radiosensitizers: A "Kinetic Competition" Between NO and NO Losses.

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 NO losses.

"Smart Decomposition" of Cyclic Alanine-Alanine Dipeptide by VUV Radiation: A Seed for the Synthesis of Biologically Relevant Species.

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.

Water-biomolecule clusters studied by photoemission spectroscopy and multilevel atomistic simulations: hydration or solvation?

The properties of mixed water-uracil nanoaggregates have been probed by core electron-photoemission measurements to investigate supramolecular assembly in the gas phase driven by weak interactions. The interpretation of the measurements has been assisted by multilevel atomistic simulations, based on semi-empirical tight-binding and DFT-based methods. Our protocol established a positive-feedback loop between experimental and computational techniques, which has enabled a sound and detailed atomistic description of such complex heterogeneous molecular aggregates.

Carbon and Nitrogen K-Edge NEXAFS Spectra of Indole, 2,3-Dihydro-7-azaindole, and 3-Formylindole.

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.

A general approach to study molecular fragmentation and energy redistribution after an ionizing event.

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.

VUV Photofragmentation of Chloroiodomethane: The Iso-CHI-Cl and Iso-CHCl-I Radical Cation Formation.

Dihalomethanes XCHY (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 ClCHI molecule has been explored in the photon energy range 9-21 eV using both VUV rare gas discharge lamps and synchrotron radiation.

Unravelling molecular interactions in uracil clusters by XPS measurements assisted by ab initio and tight-binding simulations.

The C, N and O 1s XPS spectra of uracil clusters in the gas phase have been measured. A new bottom-up approach, which relies on computational simulations starting from the crystallographic structure of uracil, has been adopted to interpret the measured spectra. This approach sheds light on the different molecular interactions (H-bond, π-stacking, dispersion interactions) at work in the cluster and provides a good understanding of the observed XPS chemical shifts with respect to the isolated molecule in terms of intramolecular and intermolecular screening occurring after the core-hole ionization.

Ion optics simulation of an ion beam setup coupled to an electrospray ionization source, strengths, and limitations.

A unified approach to achieve a start-to-end ion optics simulation of an ion beam apparatus coupled to an electrospray ionization source is presented. We demonstrate that simulations enable reliable information on the behavior and operation of the apparatus to be obtained, but due to the collisions with the buffer gas in the initial stages of the setup, the results concerning the kinetic energy of the ion beam must be treated with care.