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2. Efficient stabilization of cyanonaphthalene by fast radiative cooling and implications for the resilience of small PAHs in interstellar clouds

Author

Mark H. Stockett, James N. Bull, Henrik Cederquist, Suvasthika Indrajith, MingChao Ji, José E. Navarro Navarrete, Henning T. Schmidt, Henning Zettergren, and Boxing Zhu

Subjects
Science
Abstract

Abstract After decades of searching, astronomers have recently identified specific Polycyclic Aromatic Hydrocarbons (PAHs) in space. Remarkably, the observed abundance of cyanonaphthalene (CNN, C10H7CN) in the Taurus Molecular Cloud (TMC-1) is six orders of magnitude higher than expected from astrophysical modeling. Here, we report unimolecular dissociation and radiative cooling rate coefficients of the 1-CNN isomer in its cationic form. These results are based on measurements of the time-dependent neutral product emission rate and kinetic energy release distributions produced from an ensemble of internally excited 1-CNN+ studied in an environment similar to that in interstellar clouds. We find that Recurrent Fluorescence – radiative relaxation via thermally populated electronic excited states – efficiently stabilizes 1-CNN+, owing to a large enhancement of the electronic transition probability by vibronic coupling. Our results help explain the anomalous abundance of CNN in TMC-1 and challenge the widely accepted picture of rapid destruction of small PAHs in space.

Published
2023
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3. Stability of C59 Knockout Fragments from Femtoseconds to Infinity

Author

Michael Gatchell, Naemi Florin, Suvasthika Indrajith, José Eduardo Navarro Navarrete, Paul Martini, MingChao Ji, Peter Reinhed, Stefan Rosén, Ansgar Simonsson, Henrik Cederquist, Henning T. Schmidt, and Henning Zettergren

Subjects
Interstellar molecules, Fullerenes, Collision physics, Ion-storage rings, Astrophysics, QB460-466
Abstract

We have studied the stability of C _59 anions as a function of time, from their formation on femtosecond timescales to their stabilization on second timescales and beyond, using a combination of theory and experiments. The ${{\rm{C}}}_{59}^{-}$ fragments were produced in collisions between C _60 fullerene anions and neutral helium gas at a velocity of 90 km s ^−1 (corresponding to a collision energy of 166 eV in the center-of-mass frame). The fragments were then stored in a cryogenic ion beam storage ring at the DESIREE facility, where they were followed for up to 1 minute. Classical molecular dynamics simulations were used to determine the reaction cross section and the excitation energy distributions of the products formed in these collisions. We find that about 15% of the ${{\rm{C}}}_{59}^{-}$ ions initially stored in the ring are intact after about 100 ms and that this population then remains intact indefinitely. This means that C _60 fullerenes exposed to energetic atoms and ions, such as stellar winds and shock waves, will produce stable, highly reactive products, like C _59 , that are fed into interstellar chemical reaction networks.

Published
2024
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4. Efficient radiative cooling of tetracene cations C18H12+: absolute recurrent fluorescence rates as a function of internal energy

Author

Jérôme Bernard, MingChao Ji, Suvasthika Indrajith, Mark H. Stockett, José E. Navarro Navarrete, Naoko Kono, Henrik Cederquist, Serge Martin, Henning T. Schmidt, and Henning Zettergren

Subjects
General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract

High recurrent fluorescence rates of tetracene cations, C18H12, measured with two electrostatic ion rings, DESIREE and Mini-Ring, lead to much more effective radiative cooling than previously investigated PAH cations.

Published
2023

5. Cooling dynamics of energized naphthalene and azulene radical cations

Author

Jason W. L. Lee, Mark H. Stockett, Eleanor K. Ashworth, José E. Navarro Navarrete, Eva Gougoula, Diksha Garg, MingChao Ji, Boxing Zhu, Suvasthika Indrajith, Henning Zettergren, Henning T. Schmidt, and James N. Bull

Subjects
General Physics and Astronomy, ddc:530, Physical and Theoretical Chemistry
Abstract

The journal of chemical physics 158, 174305 (2023). doi:10.1063/5.0147456, Naphthalene and azulene are isomeric polycyclic aromatic hydrocarbons (PAHs) and are topical in the context of astrochemistry due to the recent discovery of substituted naphthalenes in the Taurus Molecular Cloud-1 (TMC-1). Here, the thermal- and photo-induced isomerization, dissociation, and radiative cooling dynamics of energized (vibrationally hot) naphthalene (Np$^+$) and azulene (Az$^+$) radical cations, occurring over the microsecond to seconds timescale, are investigated using a cryogenic electrostatic ion storage ring, affording “molecular cloud in a box” conditions. Measurement of the cooling dynamics and kinetic energy release distributions for neutrals formed through dissociation, until several seconds after hot ion formation, are consistent with the establishment of a rapid (sub-microsecond) Np$^+ ⇌$ Az$^+$ quasi-equilibrium. Consequently, dissociation by C$_2$H$_2$-elimination proceeds predominantly through common Az$^+$ decomposition pathways. Simulation of the isomerization, dissociation, recurrent fluorescence, and infrared cooling dynamics using a coupled master equation combined with high-level potential energy surface calculations [CCSD(T)/cc-pVTZ], reproduce the trends in the measurements. The data show that radiative cooling via recurrent fluorescence, predominately through the Np$^+$ D$_0$ ← D$_2$ transition, efficiently quenches dissociation for vibrational energies up to ≈1 eV above dissociation thresholds. Our measurements support the suggestion that small cations, such as naphthalene, may be more abundant in space than previously thought. The strategy presented in this work could be extended to fingerprint the cooling dynamics of other PAH ions for which isomerization is predicted to precede dissociation., Published by American Institute of Physics, Melville, NY

Published
2023

6. Experimental radiative cooling rates of a Polycyclic Aromatic Hydrocarbon cation

Author

José Eduardo Navarro Navarrete, James N Bull, Henrik Cederquist, Suvasthika Indrajith, Mingchao Ji, Henning Schmidt, Henning Zettergren, Boxing Zhu, and Mark H Stockett

Subjects
Physical and Theoretical Chemistry
Abstract

Several small Polycyclic Aromatic Hydrocarbons (PAHs) have been identified recently in the Taurus Molecular Cloud (TMC-1) using radio telescope observations. Reproducing the observed abundances of these molecules has been a challenge for astrochemical models. Rapid radiative cooling of PAHs by Recurrent Fluorescence (RF), the emission of optical photons from thermally populated electronically excited states, has been shown to efficiently stabilize small PAHs following ionization, augmenting their resilience in astronomical environments and helping to rationalize their observed high abundances. Here, we use a novel method to experimentally determine the radiative cooling rate of the cation of 1-cyanonaphthalene (C 10H 7CN, 1-CNN), the neutral species of which has been identified in TMC-1. Laser-induced dissociation rates and kinetic energy release distributions of 1-CNN cations isolated in a cryogenic electrostatic ion-beam storage ring are analysed to track the time evolution of the vibrational energy distribution of the initially hot ion ensemble as it cools. The measured cooling rate is in good agreement with the previously calculated RF rate coefficient. Improved measurements and models of the RF mechanism are needed to interpret astronomical observations and refine predictions of the stabilities of interstellar PAHs.

Published
2023

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

Author

Giuseppe Mattioli, Lorenzo Avaldi, Paola Bolognesi, Annarita Casavola, Filippo Morini, Thomas Van Caekenberghe, John D. Bozek, Mattea C. Castrovilli, Jacopo Chiarinelli, Alicja Domaracka, Suvasthika Indrajith, Sylvain Maclot, Aleksandar R. Milosavljević, Chiara Nicolafrancesco, Christophe Nicolas, Patrick Rousseau, Morini, Filippo/0000-0001-9293-5791, Mattioli, Giuseppe, Avaldi, Lorenzo, Bolognesi, Paola, Casavola, Annarita, MORINI, Filippo, Van Caekenberghe, Thomas, Bozek, John D., Castrovilli, Mattea C., Chiarinelli, Jacopo, Domaracka, Alicja, Indrajith, Suvasthika, Maclot, Sylvain, Milosavljevic, Aleksandar R., Nicolafrancesco, Chiara, Nicolas, Christophe, Rousseau, Patrick, Istituto di Struttura della Materia (CNR-ISM), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Hasselt University (UHasselt), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Atomes, Molécules et Agrégats (AMA), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Matériaux, Défauts et IRradiations (MADIR), Institut Lumière Matière [Villeurbanne] (ILM), Université Claude Bernard Lyon 1 (UCBL), and Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract

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. Ionization energies have been assessed on smaller clusters via a comparison between accurate wavefunction-based approaches and cost-effective DFT-based simulations, the latter of which were applied to clusters up to 12 uracil and 36 water molecules. The results confirm that (i) the bottom-up approach based on a multilevel method [Mattioli et al. Phys. Chem. Chem. Phys. 23, 1859 (2021)] to the structure of neutral clusters of unknown experimental composition converges to precise structure-property relationships and (ii) the coexistence of pure and mixed clusters in the water-uracil samples. A natural bond orbital (NBO) analysis performed on a subset of clusters highlighted the special role of H-bonds in the formation of the aggregates. The NBO analysis yields second-order perturbative energy between the H-bond donor and acceptor orbitals correlated with the calculated ionization energies. This sheds light on the role of the oxygen lone-pairs of the uracil CO group in the formation of strong H-bonds, with a stronger directionality in mixed clusters, giving a quantitative explanation for the formation of core-shell structures. 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), and it was partially supported by the CNRS PICS Project BIFACE, the International Associated Laboratory “DYNAMO,” and the PRIN 20173B72NB “Predicting and controlling the fate of bio-molecules driven by extreme-ultraviolet radiation”. C.N. is co-funded by Région Normandie and Synchrotron SOLEIL. SOLEIL support is acknowledged under Project No. 20171346. A.C. acknowledges the access to the CINECA supercomputer facility via the ISCRA C HP10C652JX Grant. F.M. and T.V.C. acknowledge the VSC (Flemish Supercomputer Center), funded by the Research Foundation-Flanders (FWO) and the Flemish Government.

Published
2023

8. Final Products of One-Electron Oxidation of Cyclic Dipeptides Containing Methionine Investigated by IRMPD Spectroscopy: Does the Free Radical Choose the Final Compound?

Author

Yining Jiang, Suvasthika Indrajith, Ariel Francis Perez Mellor, Thomas Bürgi, Marc Lecouvey, Carine Clavaguéra, Enrico Bodo, Chantal Houée-Levin, Estelle Loire, Giel Berden, Jos Oomens, Debora Scuderi, Institut de Chimie Physique (ICP), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Stockholm University, Université de Genève = University of Geneva (UNIGE), Chimie, Structures et Propriétés de Biomatériaux et d'Agents Thérapeutiques (CSPBAT), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Sorbonne Paris Nord, Università degli Studi di Roma 'La Sapienza' = Sapienza University [Rome] (UNIROMA), Radboud University [Nijmegen], van ‘t Hoff Institute for Molecular Sciences, Universiteit van Amsterdam (UvA), and Molecular Spectroscopy (HIMS, FNWI)

Subjects
FELIX Molecular Structure and Dynamics, IRMPD spectroscopy, Spectrum Analysis, -radiolysis, One-electron oxidation, cyclic peptides, Electrons, Dipeptides, Hydrogen Peroxide, Sulfenic Acids, Surfaces, Coatings and Films, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Methionine, One-electron oxidation -radiolysis IRMPD spectroscopy tandem mass spectrometry cyclic peptides, tandem mass spectrometry, Materials Chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Physical and Theoretical Chemistry, Sulfur
Abstract

Reactive oxygen species (ROS) such as hydrogen peroxide (H2O2) and the hydroxyl radical (•OH) have specific functions in biological processes, while their uncontrolled production and reactivity are known to be determining factors in pathophysiology. Methionine (Met) residues act as endogenous antioxidants, when they are oxidized into methionine sulfoxide (MetSO), thus depleting ROS and protecting the protein. We employed tandem mass spectrometry combined with IR multiple photon dissociation spectroscopy to study the oxidation induced by OH radicals produced by γradiolysis on model cyclic dipeptides c(LMetLMet), c(LMetDMet), and c(GlyMet). Our aim was to characterize the geometries of the oxidized peptides in the gas phase and to understand the relationship between the structure of the 2-center 3-electron (2c-3e) free radical formed in the first step of the oxidation process and the final compound. Density functional theory calculations were performed to characterize the lowest energy structures of the final product of oxidation and to interpret the IR spectra. Collision-induced dissociation tandem mass spectrometry (CID-MS2) experiments of oxidized c(LMetLMet)H+ and c(LMetDMet)H+ led to the loss of one or two oxidized sulfenic acid molecules, indicating that the addition of one or two oxygen atoms occurs on the sulfur atom of both methionine side chains and no sulfone formation was observed. The CID-MS2 fragmentation mass spectrum of oxidized c(GlyMet)H+ showed only the loss of one oxidized sulfenic acid molecule. Thus, the final products of oxidation are the same regardless of the structure of the precursor sulfur-centered free radical.

Published
2022

9. Spontaneous and photo-induced decay processes of WF

Author

Hubert, Gnaser, Martin, Martschini, David, Leimbach, Julia, Karls, Dag, Hanstorp, Suvasthika, Indrajith, Mingchao, Ji, Paul, Martini, Ansgar, Simonsson, Henning, Zettergren, Henning T, Schmidt, and Robin, Golser

Abstract

Spontaneous and photo-induced decay processes of HfF

Published
2022

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

Author

Giuseppe, Mattioli, Lorenzo, Avaldi, Paola, Bolognesi, John D, Bozek, Mattea C, Castrovilli, Jacopo, Chiarinelli, Alicja, Domaracka, Suvasthika, Indrajith, Sylvain, Maclot, Aleksandar R, Milosavljević, Chiara, Nicolafrancesco, and Patrick, Rousseau

Subjects
Models, Molecular, Spectrometry, Fluorescence, Photoelectron Spectroscopy, Solvents, Thermodynamics, Water, Hydrogen Bonding, Uracil, Hydrophobic and Hydrophilic Interactions, Density Functional Theory, Nanostructures
Abstract

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. Among biomolecules, uracil offers interesting and generalized skeletal features; its structure encompasses an alternation of hydrophilic H-bond donor and acceptor sites and hydrophobic moieties, typical in biomolecular systems, that induces a supramolecular core-shell-like organization of the mixed clusters with a water core and an uracil shell. This structure is far from typical models of both solid-state hydration, with water molecules in defined positions, or liquid solvation, where disconnected uracil molecules are completely surrounded by water.

Published
2021

12. A cluster source for photoelectron spectroscopy in VUV and X-ray ranges

Author

E. Robert, J. F. Gil, Christophe Nicolas, Laurent Nahon, John D. Bozek, Aleksandar R. Milosavljević, Chiara Nicolafrancesco, Suvasthika Indrajith, Patrick Rousseau, J.M. Ramillon, Sebastian Hartweg, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Normandie Université (NU), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Atomes, Molécules et Agrégats (AMA), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN)

Subjects
[PHYS]Physics [physics], Materials science, Valence (chemistry), X-ray, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Mass spectrometry, 01 natural sciences, Atomic and Molecular Physics, and Optics, Synchrotron, Spectral line, 0104 chemical sciences, law.invention, X-ray photoelectron spectroscopy, law, Physics::Atomic and Molecular Clusters, Cluster (physics), Physics::Accelerator Physics, Atomic physics, 0210 nano-technology, Molecular beam
Abstract

A detailed description of a custom-made gas aggregation cluster source is given as well as of its coupling to permanent molecular beam end-stations of the beamlines DESIRS and PLEIADES at the French national facility synchrotron SOLEIL. Using (hydrated) hypoxanthine clusters as a case study, the production of clusters with different source parameters is discussed based on Vacuum Ultra-Violet (VUV) mass spectrometry. The ability of the cluster source to perform photoelectron spectroscopy is illustrated by photoelectron spectra obtained for valence and core shells.

Published
2021

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

Author

Paola Bolognesi, Sergio Díaz-Tendero, Patrick Rousseau, Ewa Erdmann, Jacopo Chiarinelli, Suvasthika Indrajith, Bernd A. Huber, Marta Łabuda, Alicja Domaracka, Robert Richter, Manuel Alcamí, Néstor F. Aguirre, Lorenzo Avaldi, Gdańsk University of Technology (GUT), Universidad Autonoma de Madrid (UAM), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Université de Caen Normandie (UNICAEN), Istituto di Struttura della Materia (CNR-ISM), Consiglio Nazionale delle Ricerche [Roma] (CNR), Centre National de la Recherche Scientifique (CNRS), Elettra Sincrotrone Trieste, Universidad Autónoma de Madrid (UAM), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), and National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR)

Subjects
Physics, [PHYS.PHYS]Physics [physics]/Physics [physics], 010304 chemical physics, Internal energy, furan, education, General Physics and Astronomy, Photoionization, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Molecular physics, Dissociation (chemistry), PEPICO, 0104 chemical sciences, Ion, M3C, Fragmentation (mass spectrometry), Ionization, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Mass spectrum, Redistribution (chemistry), Physical and Theoretical Chemistry
Abstract

International audience; 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 photoelectronphotoion coincidence experiments and the different mass spectra obtained when ions ranging from Ar + to Xe 25+ 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.

Published
2021

14. Vibrationally Mediated Stabilization of Electrons in Nonpolar Matter

Author

Alicja Domaracka, Štěpán Sršeň, Jaroslav Kočišek, Jakub Med, Patrick Rousseau, Juraj Fedor, Petr Slavíček, Suvasthika Indrajith, Michal Fárník, Department of Physical Chemistry, University of Chemistry and Technology, Prague, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, 010304 chemical physics, Electron energy loss spectroscopy, Quantum dynamics, [PHYS.PHYS.PHYS-ATM-PH]Physics [physics]/Physics [physics]/Atomic and Molecular Clusters [physics.atm-clus], Solvation, Electron, 010402 general chemistry, Solvated electron, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Ion, Chemical physics, Molecular vibration, 0103 physical sciences, Path integral molecular dynamics, General Materials Science, Physical and Theoretical Chemistry, Physics::Chemical Physics
Abstract

International audience; We explore solvation of electrons in nonpolar matter, here represented by butadiene clusters. Isolated butadiene supports only the existence of transient anions (resonances). Two-dimensional electron energy loss spectroscopy shows that the resonances lead to an efficient vibrational excitation of butadiene, which can result into the almost complete loss of energy of the interacting electron. Cluster-beam experiments show that molecular clusters of butadiene form stable anions, however only at sizes of more than 9 molecular units. We have calculated the distribution of electron affinities of clusters using classical and path integral molecular dynamics simulations. There is almost a continuous transition from the resonant to the bound anions with an increase in cluster size. The comparison of the classical and quantum dynamics reveals that the electron binding is strongly supported by molecular vibrations, brought about by nuclear zero-point motion and thermal agitation. We also inspected the structure of the solvated electron, finding it well localized.

Published
2020

15. Infrared-Assisted Synthesis of Prebiotic Glycine

Author

Ariel Pérez-Mellor, Jean-Xavier Bardaud, Debora Scuderi, Suvasthika Indrajith, Riccardo Spezia, Yannick Jeanvoine, Antonio Largo, Joël Lemaire, Institut de Chimie Physique (ICP), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Normale Supérieure Paris-Saclay (ENS Paris Saclay), Universidad de Valladolid [Valladolid] (UVa), Laboratoire Analyse, Modélisation et Matériaux pour la Biologie et l'Environnement (LAMBE - UMR 8587), Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-CY Cergy Paris Université (CY), Laboratoire de chimie théorique (LCT), and Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)

Subjects
IR-assisted synthesis, prebiotic chemistry, Infrared, complex organic molecules, 02 engineering and technology, 010402 general chemistry, Photochemistry, Mass spectrometry, 01 natural sciences, Acetic acid, chemistry.chemical_compound, ion-molecule reactions, Hydroxylamine, Fragmentation (mass spectrometry), Irradiation, Physical and Theoretical Chemistry, 021001 nanoscience & nanotechnology, Atomic and Molecular Physics, and Optics, 3. Good health, 0104 chemical sciences, Moléculas orgánicas complejas, chemistry, Molecular vibration, Glycine, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], 0210 nano-technology, glycine
Abstract

Producción Científica, A novel approach has been developed to synthesize complex organic molecules (COMs) relevant to prebiotic chemistry, using infrared (IR) radiation to trigger the reaction. An original laboratory reactor working at low gas density and using IR irradiation was developed. In this way, glycine, the simplest brick of life, has been synthesized by assisting ion–molecule reaction with IR laser light. The ion‐molecule complex constituted by acetic acid and hydroxylamine was formed in a mass spectrometer reactor and then irradiated with IR photons. As photoproducts, we obtained both glycine structures and some of its isomers. Anharmonic vibrational frequency calculations and fragmentation dynamics simulations allow for a better interpretation of the experimental data. This novel approach can be now extended to study other new synthetic pathways responsible for the formation of further COMs also with potential prebiotic relevance., ANR DynBioReact. Grant Number: ANR-14-CE06-0029-01, CNRS program INFINITI (project ASTROCOL). Grant Number: 2013-0562-T, Chiraux IRUV (RTRA), Labex Palm, Paris Scalay

Published
2020

16. Interaction of hydantoin with solar wind minority ions: O6+ and He2+

Author

P. Moretto-Capelle, Julie Renoud, Alicja Domaracka, Suvasthika Indrajith, Bernd A. Huber, Patrick Rousseau, Jean-Philippe Champeaux, Interactions Ions-Matière (LCAR) (I²M), Laboratoire Collisions Agrégats Réactivité (LCAR), Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université de Toulouse (UT)-Université de Toulouse (UT)-Centre National de la Recherche Scientifique (CNRS), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National des Sciences Appliquées - Toulouse (INSA Toulouse), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées, Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Systèmes Atomiques et Moléculaires Complexes (IRSAMC), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)

Subjects
Physics, Astrochemistry, Double ionization, General Physics and Astronomy, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, Reaction coordinate, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Ionization, 0103 physical sciences, Mass spectrum, Molecule, Density functional theory, Physical and Theoretical Chemistry, 0210 nano-technology, 010303 astronomy & astrophysics
Abstract

The laboratory study of prebiotic molecules interacting with solar wind ions is important to understand their role in the emergence of life in the complex context of the astrochemistry of circumstellar environments. In this work, we present the first study of the interaction of hydantoin (C3N2O2H4, 100 a.m.u.) with solar wind minority multi-charged ions: O6+ at 30 keV and He2+ at 8 keV. The fragmentation mass spectra as well as correlation maps resulting from the interaction are presented and discussed in this paper. Prompt and delayed dissociations from metastable states of the ionized molecule have been observed and the corresponding lifetimes measured. Experimental results are completed by quantum Density Functional Theory (DFT) calculations for energies, structures and dynamics (Internal Reaction Coordinates and Dynamic Reaction Coordinates) of the molecule for its different reachable charge states and the major observed fragmentation pathways. These calculations show that the molecule can only support two charges before spontaneously dissociating in agreement with the experimental observations. Calculations also demonstrate that hydantoin's ring opens after double ionization of the molecule which may enhance its reactivity in the background of biological molecule formation in a cirmcumstellar environment. For the major experimentally observed fragmentations (like 44 a.m.u./56 a.m.u. dissociation), Internal Reaction Coordinate (IRC) calculations were performed pointing out for example the important role of hydrogen transfer in the fragmentation processes.

Published
2020

17. Dissociation dynamics of the diamondoid adamantane upon photoionization by XUV femtosecond pulses

Author

Jan Lahl, Sergio Díaz-Tendero, Néstor F. Aguirre, Fabian Brunner, Patrick Rousseau, Hélène Coudert-Alteirac, Piotr Rudawski, Sylvain Maclot, Bernd A. Huber, Suvasthika Indrajith, Hampus Wikmark, Per Johnsson, Jasper Peschel, UAM. Departamento de Física de la Materia Condensada, UAM. Departamento de Química, Lund University [Lund], Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Atomes, Molécules et Agrégats (AMA), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Universidad Autónoma de Madrid (UAM), and Normandie Université (NU)

Subjects
Materials science, Adamantane, FOS: Physical sciences, lcsh:Medicine, Photoionization, Coulomb repulsion-driven fragmentation, Diamondoid, 01 natural sciences, Dissociation (chemistry), Article, chemistry.chemical_compound, Fragmentation (mass spectrometry), Physics - Chemical Physics, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Physics::Chemical Physics, 010306 general physics, lcsh:Science, [PHYS]Physics [physics], Chemical Physics (physics.chem-ph), Ultraviolet femtosecond pulses, [PHYS.PHYS.PHYS-OPTICS]Physics [physics]/Physics [physics]/Optics [physics.optics], Multidisciplinary, 010304 chemical physics, Attosecond science, [PHYS.PHYS.PHYS-ATM-PH]Physics [physics]/Physics [physics]/Atomic and Molecular Clusters [physics.atm-clus], Photodissociation, lcsh:R, Física, Atomic and molecular interactions with photons, Química, [PHYS.PHYS.PHYS-SPACE-PH]Physics [physics]/Physics [physics]/Space Physics [physics.space-ph], 3. Good health, Dication, chemistry, Chemical physics, Diamondoid adamantane, Femtosecond, lcsh:Q, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract

This work presents a photodissociation study of the diamondoid adamantane using extreme ultraviolet femtosecond pulses. The fragmentation dynamics of the dication is unraveled by the use of advanced ion and electron spectroscopy giving access to the dissociation channels as well as their energetics. To get insight into the fragmentation dynamics, we use a theoretical approach combining potential energy surface determination, statistical fragmentation methods and molecular dynamics simulations. We demonstrate that the dissociation dynamics of adamantane dications takes place in a two-step process: barrierless cage opening followed by Coulomb repulsion-driven fragmentation, This research was supported by the Swedish Research Council, the Swedish Foundation for Strategic Research and the Crafoord Foundation. This project has received funding from the European Union’s Horizon 2020 research and innovation program under the Marie Sklodowska-Curie Grant Agreement No. 641789 MEDEA and under grant agreement no 654148 Laserlab-Europe. The research was conducted in the framework of the International Associated Laboratory (LIA) Fragmentation DYNAmics of complex MOlecular systems - DYNAMO, funded by the Centre National de la Recherche Scientifique (CNRS). The authors acknowledge the generous allocation of computer time at the Centro de Computación Científica at the Universidad Autónoma de Madrid (CCC-UAM). This work was partially supported by the project CTQ2016-76061-P of the Spanish Ministerio de Economía y Competitividad (MINECO). Financial support from the MINECO through the "María de Maeztu” Program for Units of Excellence in R&D (MDM-2014-0377) is also acknowledged

Published
2020

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

Author

Patrick Rousseau, John D. Bozek, Paola Bolognesi, Mattea Carmen Castrovilli, Aleksandar R. Milosavljević, Lorenzo Avaldi, Suvasthika Indrajith, Chiara Nicolafrancesco, Giuseppe Mattioli, Alicja Domaracka, Christophe Nicolas, Sylvain Maclot, Jacopo Chiarinelli, Istituto di Struttura della Materia (CNR-ISM), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Lund University [Lund], Royal Institute of Technology [Stockholm] (KTH ), Consiglio Nazionale delle Ricerche [Roma] (CNR), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
0301 basic medicine, Materials science, Chemical physics, Ab initio, lcsh:Medicine, Article, 03 medical and health sciences, Molecular dynamics, 0302 clinical medicine, X-ray photoelectron spectroscopy, Cluster (physics), XPS, Molecule, lcsh:Science, Quantitative Biology::Biomolecules, Multidisciplinary, Weakly bonded systems, Chemical shift, Intermolecular force, lcsh:R, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, 030104 developmental biology, Physical chemistry, Cluster, Intramolecular force, lcsh:Q, 030217 neurology & neurosurgery
Abstract

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. The proposed bottom-up approach, reasonably expensive in terms of computational resources, has been validated by finite-temperature molecular dynamics simulations of clusters composed of up to fifty molecules.

Published
2020

19. Determination of energy-transfer distributions in ionizing ion-molecule collisions

Author

Paola Bolognesi, Manuel Alcamí, Suvasthika Indrajith, Patrick Rousseau, Jacopo Chiarinelli, Alicja Domaracka, Bernd A. Huber, Marta Łabuda, Sergio Díaz-Tendero, Ewa Erdmann, Lorenzo Avaldi, Néstor F. Aguirre, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Istituto di Struttura della Materia (CNR-ISM), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Departamento de Qímica, Módulo 13, Universidad Autónoma de Madrid, Departamento de Qímica, IMAFF, Laboratoire des collisions atomiques et moléculaires (LCAM), and Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Physics, [PHYS]Physics [physics], History, 010304 chemical physics, Energy transfer, 01 natural sciences, Computer Science Applications, Education, Ionizing radiation, Ion, 0103 physical sciences, Molecule, Atomic physics, 010306 general physics
Abstract

Synopsis The main objective of this study is to determine the energy transfer occuring in ion-molecule collisions. In order to solve this problem, we followed two approaches; the first one by validating a purely experimental method and the second one by testing a new theoretical model M3C (Microcanonical Metropolis Monte Carlo).

Published
2020

20. Infra-Red Assisted Synthesis of Prebiotic Glycine

Author

Jean-Xavier Bardaud, Suvasthika Indrajith, Joël Lemaire, Debora Scuderi, Ariel Pérez-Mellor, Yannick Jeanvoine, Riccardo Spezia, and Antonio Largo

Subjects
Interstellar medium, Work (thermodynamics), chemistry.chemical_compound, Hydroxylamine, Chemical physics, Chemistry, law, Infrared, Molecule, Protonation, Laser, Quantum chemistry, law.invention
Abstract

In the present study, we have shown for the first time how glycine can be synthesized under prebiotic-like conditions using an Infra-Red laser to trigger the reaction. In particular, we observed that in the low-density conditions it can be obtained from simple ion-molecule reactions of acetic acid and protonated hydroxylamine. This reaction, studied years ago in more dense conditions [J. Am. Chem. Soc. 2007, 129, 9910-9917R], was the center of a controversy, since accurate quantum chemistry calculations have shown that it is not barrierless [Astrophys. J. 2012, 748, 99] such that a source of energy is needed. In space, and more in general in prebiotic conditions (interstellar medium, comets, asteroids) temperature is very low but the photon density can be important. Here we propose a way of synthesizing such complex organic molecule in a very low-pressure environment (about 10-3 mbar). This way of forming complex organic molecule is of relevance also beyond the prebiotic interest of finding a scenario which was at the origin of the synthesis of such molecules. In fact our work proposes a new way of assisting reactions using IR radiation. Only few cases were found in which IR can trigger complex reactions (i.e. not simple dissociations) while there is a clear interest of using such low-energy radiation. This study will be at the basis of new researches devoted to find other reactions which can be assisted by IR laser.

Published
2019

21. Decomposition of Iron Pentacarbonyl Induced by Singly and Multiply Charged Ions and Implications for Focused Ion Beam-Induced Deposition

Author

Chiara Nicolafrancesco, Alicja Domaracka, Kateryna Grygoryeva, Patrick Rousseau, Barbora Sedmidubská, Suvasthika Indrajith, Bernd A. Huber, Juraj Fedor, Pamir Nag, Jaroslav Kočišek, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), and Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Projectile, Astrophysics::High Energy Astrophysical Phenomena, 02 engineering and technology, Substrate (electronics), 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Focused ion beam, Decomposition, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ion, Iron pentacarbonyl, chemistry.chemical_compound, General Energy, Nanolithography, chemistry, Physics::Plasma Physics, Chemical physics, Deposition (phase transition), Physical and Theoretical Chemistry, [PHYS.COND]Physics [physics]/Condensed Matter [cond-mat], 0210 nano-technology
Abstract

International audience; Focused ion beams are becoming important tools in nanofabrication.The underlying physical processes in the substrate were already explored for severalprojectile ions. However, studies of ion interaction with precursor molecules forbeam-assisted deposition are almost nonexistent. Here, we explore the interaction ofvarious projectile ions with iron pentacarbonyl. We report fragmentation patterns ofisolated gas-phase iron pentacarbonyl after interaction with 4He+ at a collisionenergy of 16 keV, 4He2+ at 16 keV, 20Ne+ at 6 keV, 20Ne4+ at 40 keV, 40Ar+ at 3 keV,40Ar3+ at 21 keV, 84Kr3+ at 12 keV, and 84Kr17+ at 255 keV. These projectiles coverinteraction regimes ranging from collisions dominated by nuclear stopping throughcollisions dominated by electronic stopping to soft resonant electron-captureinteractions. We report a surprising efficiency of Ne+ in the Fe(CO)5decomposition. The interaction with multiply charged ions results in a highercontent of parent ions and slow metastable fragmentation due to the electroncaptureprocess. The release of CO groups during the decomposition process seems to take off a significant amount of energy.The fragmentation mechanism may be described as Fe being trapped within a CO cluster.

Published
2019

22. Understanding the formation of metastable furan dication in collisions with ions

Author

Manuel Alcamí, Sergio Díaz-Tendero, Suvasthika Indrajith, Néstor F. Aguirre, Ewa Erdmann, Paola Bolognesi, Jacopo Chiarinelli, Patrick Rousseau, Lorenzo Avaldi, Marta Łabuda, Alicja Domaracka, and Bernd A. Huber

Subjects
History, chemistry.chemical_compound, chemistry, Furan, Metastability, Photochemistry, Computer Science Applications, Education, Dication, Ion
Abstract

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.

Published
2020

23. Energetic processing of hydrocarbons molecular species by ionizing radiation towards the formation of cyclic species

Author

Patrick Rousseau, J Kočišekt, Suvasthika Indrajith, Alicja Domaracka, Bernd A. Huber, Centre de recherche sur les Ions, les MAtériaux et la Photonique (CIMAP - UMR 6252), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), and Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], History, Photon, Materials science, Electron, Molecular physics, Computer Science Applications, Education, Ion, Ionizing radiation
Abstract

Synopsis Here we report on experimental studies of the collisions between butadiene clusters and three different ionizing radiation sources: 70 eV electrons, 270 nm photons and 3 keV Ar+ ions. New molecular species are produced by growth mechanism inside of clusters.

Published
2020

24. Electron Attachment to Microhydrated Deoxycytidine Monophosphate

Author

Jaroslav Kočišek, Juraj Fedor, Suvasthika Indrajith, Barbora Sedmidubská, and Michal Fárník

Subjects
chemistry.chemical_classification, Models, Molecular, Aqueous solution, 010405 organic chemistry, Chemistry, Molecular Conformation, Glycosidic bond, Deoxycytidine monophosphate, Deoxycytidine Monophosphate, 010402 general chemistry, Photochemistry, 01 natural sciences, Electron transport chain, Dissociation (chemistry), 0104 chemical sciences, Surfaces, Coatings and Films, Electron Transport, chemistry.chemical_compound, Phosphodiester bond, Materials Chemistry, Molecule, Physical and Theoretical Chemistry, DNA
Abstract

DNA constituents are effectively decomposed via dissociative electron attachment (DEA). However, the DEA contribution to radiation damage in living tissues is a subject of ongoing discussion. We address an essential question, how aqueous environment influences the DEA to DNA. In particular, we report experimental fragmentation patterns for DEA to microhydrated 2-deoxycytidine 5-monophosphate (dCMP). Isolated dCMP was previously set as a model to describe mechanisms of DNA-strand breaks induced by secondary electrons and decomposes primarily by dissociation of the C-O phosphoester bond. We show that hydrated molecules decompose via dissociation of the C-N glycosidic bond followed by dissociation of the P-O bond. This significant change of the proposed mechanism can be interpreted by a reactive role of water in the postattachment dynamics. Comparison of the fragmentation with previous macroscopic irradiation studies suggests that the actual contribution of DEA to DNA radiation damage in living tissue is rather small.

Published
2018

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