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11 results on '"Institut Rayonnement Matière de Saclay ( IRAMIS )"'

1. Where do the counterions go? Tip-induced dissociation of self-assembled triazatriangulenium-based molecules on Au(111)

Author

Olivier Pluchery, Yannick J. Dappe, Thomas Huhn, Elke Scheer, Dmytro Sysoiev, S. V. Snegir, Universität Konstanz, Groupe Modélisation et Théorie (GMT), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences (IOCB / CAS), Czech Academy of Sciences [Prague] (CAS), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay

Subjects
inorganic chemicals, Materials science, General Physics and Astronomy, 02 engineering and technology, Substrate (electronics), 010402 general chemistry, 01 natural sciences, Dissociation (chemistry), law.invention, Metal, law, Electric field, Monolayer, Molecule, ddc:530, Physical and Theoretical Chemistry, chemistry.chemical_classification, 021001 nanoscience & nanotechnology, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, self-assembled monolayers, triazatriangulenium (TATA), chemistry, Chemical physics, visual_art, visual_art.visual_art_medium, Counterion, Scanning tunneling microscope, 0210 nano-technology
Abstract

Chemical coupling of functional molecules on top of the so-called platform molecules allows the formation of functional self-assembled monolayers (SAMs). An often-used example of such a platform is triazatriangulenium (TATA), which features an extended aromatic core providing good electronic contact to the underlying metal surface. Here, we present a study of the SAM formation of a TATA platform on Au(111) employing scanning tunneling microscopy (STM) under ambient atmospheric conditions. In solution, the TATA platform is stabilized by BF4 counterions, while after deposition on a gold substrate, the localization of the BF4 counterions remains unknown. We used 1,2,4-trichlorobenzene as a solvent of TATA–BF4 to induce SAM formation on a heated (∼50 °C) Au substrate. We show by STM how to detect and distinguish TATA–BF4 from TATA platforms, which lost their BF4 counterions. Finally, we observe a change of the counterion position on the SAM during the STM scanning, which we explain by an electric-field-induced decrease of the electrostatic interaction in TATA–BF4 on the surface. We applied DFT calculations to reveal the influence of the gold lattice and the electric field of the STM tip on the stability of TATA–BF4 physisorbed on the surface. published

Published
2021

2. Multiscale time-resolved fluorescence study of a glycogen phosphorylase inhibitor combined with quantum chemistry calculations

Author

Dimitra Markovitsi, Konstantinos F. Mavreas, Michael Mamais, Thanasis Gimisis, Filippo Monti, Evangelia D. Chrysina, Alessandro Venturini, Thomas Gustavsson, Valentin Maffeis, Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN UMR 3685), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), National and Kapodistrian University of Athens (NKUA), Istituto per la Sintesi Organica e la Fotoreattività (ISOF-CNR), National Research Council of Italy | Consiglio Nazionale delle Ricerche (CNR), Dynamique et Interactions en phase Condensée (DICO), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), National Hellenic Research Foundation [Athens], Istituto CNR per la Sintesi Organica e Fotoreattivita (ISOF), European Project: 284464,EC:FP7:INFRA,FP7-INFRASTRUCTURES-2011-1,LASERLAB-EUROPE(2012), Laboratoire Innovation en Chimie des Surfaces et NanoSciences (LICSEN), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Consiglio Nazionale delle Ricerche (CNR), Biomolécules Excitées (DICO), and Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Inhibitor, Population, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, DFT, Benzoates, Fluorescence spectroscopy, Glycogen phosphorylase, chemistry.chemical_compound, Computational chemistry, Physical and Theoretical Chemistry, Enzyme Inhibitors, education, Conformational isomerism, education.field_of_study, Chemistry, Glycogen Phosphorylase, 021001 nanoscience & nanotechnology, Fluorescence, Multiscale fluorescence, 3. Good health, 0104 chemical sciences, Acridone, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Spectrometry, Fluorescence, Excited state, Quantum Theory, Thermodynamics, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Time-resolved spectroscopy, 0210 nano-technology, Acridones
Abstract

International audience; A fluorescence study of N1-(β-D-glucopyranosyl)-N4-[2-acridin-9(10H)-onyl]-cytosine (GLAC), the first fluorescent potent inhibitor of glycogen phosphorylase (GP), in neutral aqueous solution, is presented herein. Quantum chemistry (TD-DFT) calculations show the existence of several conformers both in the ground and first excited states. They result from rotations of the acridone and cytosine moieties around an NH bridge which may lead to the formation of non-emitting charge-transfer states. The fingerprints of various conformers have been detected by time-resolved fluorescence spectroscopy (fluorescence upconversion and time-correlated single photon counting) and identified using as criteria their energy, polarization and relative population resulting from computations. Such an analysis should contribute to the design of new GP inhibitors with better fluorescence properties, suitable for imaging applications.

Published
2019

3. Vibrational mode assignment of finite temperature infrared spectra using the AMOEBA polarizable force field

Author

Jean-Pierre Dognon, Gilles Ohanessian, Carine Clavaguéra, Florian Thaunay, Laboratoire de chimie moléculaire (LCM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-École polytechnique (X), Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF) (LCMCE), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), École polytechnique (X)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structure et Dynamique par Résonance Magnétique (LCF) (LSDRM), and Laboratoire des mécanismes réactionnels (DCMR)

Subjects
Quantitative Biology::Biomolecules, Spectrophotometry, Infrared, Chemistry, Anharmonicity, Molecular Conformation, Temperature, General Physics and Astronomy, Infrared spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, Dipeptides, Molecular Dynamics Simulation, Molecular physics, Molecular conformation, Force field (chemistry), [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Molecular dynamics, Polarizability, Computational chemistry, Molecular vibration, Physics::Chemical Physics, Physical and Theoretical Chemistry
Abstract

International audience; The calculation of infrared spectra by molecular dynamics simulations based on the AMOEBA polarizable force field has recently been demonstrated [Semrouni et al., J. Chem. Theory Comput., 2014, 10, 3190]. While this approach allows access to temperature and anharmonicity effects, band assignment requires additional tools, which we describe in this paper. The Driven Molecular Dynamics approach, originally developed by Bowman, Kaledin et al. [Bowman et al. J. Chem. Phys., 2003, 119, 646, Kaledin et al. J. Chem. Phys., 2004, 121, 5646] has been adapted and associated with AMOEBA. Its advantages and limitations are described. The IR spectrum of the Ac-Phe-Ala-NH 2 model peptide is analyzed in detail. In addition to differentiation of conformations by reproducing frequency shifts due to non-covalent interactions, DMD allows visualizing the temperature-dependent vibrational modes.

Published
2015

4. The effect of myoglobin crowding on the dynamics of water: an infrared study

Author

Serge Pin, Géraldine Klein, Pascal Roy, Stanislas Pommeret, Stéphanie Devineau, Jean Philippe Renault, S. Le Caër, Winfried Leibl, Manuela Lima, Daniel Ortiz, J.-B. Brubach, Roberto Righini, Laboratoire Interdisciplinaire sur l'Organisation Nanométrique et Supramoléculaire (LIONS), Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M) (NIMBE UMR 3685), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Firenze = University of Florence (UniFI), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire Claude Fréjacques (LCF - URA 331), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), Système membranaires, photobiologie, stress et détoxication (SMPSD), ANR-10-INBS-0005,FRISBI,Infrastructure Française pour la Biologie Structurale Intégrée(2010), Università degli Studi di Firenze = University of Florence [Firenze] (UNIFI), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Institut Rayonnement Matière de Saclay (IRAMIS), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Properties of water, Infrared, Analytical chemistry, General Physics and Astronomy, Infrared spectroscopy, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Spectroscopy, Fourier Transform Infrared, Vibrational energy relaxation, Molecule, Physical and Theoretical Chemistry, Range (particle radiation), Quantitative Biology::Biomolecules, Myoglobin, Anharmonicity, Temperature, Water, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, 0210 nano-technology
Abstract

International audience; Solutions containing 8 and 32 wt% myoglobin are studied by means of infrared spectroscopy, as a function of temperature (290 K and lower temperatures), in the mid- and far-infrared spectral range. Moreover, ultrafast time-resolved infrared measurements are performed at ambient temperature in the O-D stretching region. The results evidence that the vibrational properties of water remain the same in these myoglobin solutions (anharmonicity, vibrational relaxation lifetime...) and in neat water. However, the collective properties of the water molecules are significantly affected by the presence of the protein: the orientational time increases, the solid-liquid transition is affected in the most concentrated solution and the dynamical transition of the protein is observed, from the point of view of water, even in the least concentrated solution, proving that the water and myoglobin dynamics are coupled.

Published
2014

5. Phthalocyanine reactivity and interaction on the 6H-SiC(0001)-(3 × 3) surface investigated by core-level experiments and simulations

Author

Anu Baby, Guillaume Marcaud, Yannick J. Dappe, Marie D’Angelo, Jean-Louis Cantin, Mathieu G. Silly, Guido Fratesi, Università degli Studi di Milano-Bicocca = University of Milano-Bicocca (UNIMIB), Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Groupe Modélisation et Théorie (GMT), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Università degli Studi di Milano = University of Milan (UNIMI), and European Project: 654360,H2020,H2020-INFRAIA-2014-2015,NFFA-Europe(2015)

Subjects
[PHYS]Physics [physics], General Physics and Astronomy, Physical and Theoretical Chemistry
Abstract

International audience; The adsorption of phthalocyanine (H$_2$ Pc) on the 6H-SiC(0001)-(3 x 3) surface is investigated using X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure spectroscopy (NEXAFS), and density functional theory (DFT) calculations. Spectral features are tracked from the submonolayer to the multilayer growth regime, observing a significant modification of spectroscopic signals at low coverage with respect to the multilayer films, where molecules are weakly interacting. Molecules stay nearly flat on the surface at the mono and submonolayers. Previously proposed adsorption models, where the molecule binds by two N atoms to corresponding Si adatoms, do not reproduce the experimental spectra at the submonolayer coverage. We find instead that another adsorption model where the molecule replaces the two central H atoms by a Si adatom, effectively forming Si-phthalocyanine (SiPc), is both energetically more stable and yields in combination a better agreement between the experimental and simulated spectra. This suggests that the 6H-SiC(0001)-(3 Â 3) surface may be a candidate substrate for the on-surface synthesis of SiPc molecules.

Published
2022

6. Stepwise dissociation of ion pairs by water molecules: cation-dependent separation mechanisms between carboxylate and alkali-earth metal ions

Author

Jeremy Donon, Jean-Xavier Bardaud, Valérie Brenner, Shun-Ichi Ishiuchi, Masaaki Fujii, Eric Gloaguen, Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), LUmière et MOlécules (LUMO), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Structures BioMoléculaires (SBM), Tokyo Institute of Technology [Tokyo] (TITECH), ANR-16-CE29-0017,IONPAIRS,Spectroscopie de paires d'ions isolées et microsolvatées(2016), and ANR-20-CE29-0016,VAPOBIO,Evaporation en fluide supercritique pour des études spectroscopiques et chromatographiques approfondies de systèmes biomoléculaires neutres(2020)

Subjects
[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Cations, Metals, Alkaline Earth, Carboxylic Acids, General Physics and Astronomy, Water, Physical and Theoretical Chemistry
Abstract

The first steps of ion dissociation in microhydrated H2-tagged ion pairs (Ca2+, AcO−)(H2O)n=0–8 and (Ba2+, AcO−)(H2O)n=0–5 are revealed by IR photodissociation laser spectroscopy and DFT-D frequency calculations.

Published
2022

7. The surprisingly high ligation energy of CO to ruthenium porphyrins

Author

Laurent Nahon, Niloufar Shafizadeh, Satchin Soorkia, Séverine Boyé-Péronne, Gustavo A. Garcia, Shufeng Chen, Aurélien de la Lande, Lionel Poisson, Barbara Cunha de Miranda, Benoît Soep, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Dynamique Réactionnelle (DyR), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), ANR-11-IDEX-0003,IPS,Idex Paris-Saclay(2011), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Spin states, 010405 organic chemistry, Chemistry, Ligand, Binding energy, General Physics and Astronomy, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ruthenium, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Tetraphenylporphyrin, Physical chemistry, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Singlet state, Physical and Theoretical Chemistry, Bond energy, Ionization energy
Abstract

A combined theoretical and experimental approach has been used to investigate the binding energy of a ruthenium metalloporphyrin ligated with CO, ruthenium tetraphenylporphyrin [RuII TPP], in the RuII oxidation degree. Measurements performed with VUV ionization using the DESIRS beamline at Synchrotron SOLEIL led to adiabatic ionization energies of [RuII TPP] and its complex with CO, [RuII TPP–CO], of 6.48 ± 0.03 eV and 6.60 ± 0.03 eV, respectively, while the ion dissociation threshold of [RuII TPP–CO]+ is measured to be 8.36 ± 0.03 eV using the ground-state neutral complex. These experimental data are used to derive the binding energies of the CO ligand in neutral and cationic complexes (1.88 ± 0.06 eV and 1.76 ± 0.06 eV, respectively) using a Born–Haber cycle. Density functional theory calculations, in very satisfactory agreement with the experimental results, help to get insights into the metal–ligand bond. Notably, the high ligation energies can be rationalized in terms of the ruthenium orbital structure, which is singular compared to that of the iron atom. Thus, beyond indications of a strengthening of the Ru–CO bond due to the decrease in the CO vibrational frequency in the complex as compared to the Fe–CO bond, high-level calculations are essential to accurately describe the metal ligand (CO) bond and show that the Ru–CO bond energy is strongly affected by the splitting of triplet and singlet spin states in uncomplexed [Ru TPP].

Published
2018

8. Self-trapping relaxation decay investigated by time-resolved photoelectron spectroscopy

Author

Benoît Soep, Aude Lietard, Jean-Michel Mestdagh, Vincent Mazet, Giovanni Piani, Marc-André Gaveau, Sylvain Faisan, Lionel Poisson, M. Briant, Dynamique Réactionnelle (DyR), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des sciences de l'ingénieur, de l'informatique et de l'imagerie (ICube), École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Université de Strasbourg (UNISTRA)-Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Institut National de Recherche en Informatique et en Automatique (Inria)-Les Hôpitaux Universitaires de Strasbourg (HUS)-Centre National de la Recherche Scientifique (CNRS)-Matériaux et Nanosciences Grand-Est (MNGE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences Appliquées - Strasbourg (INSA Strasbourg), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-École Nationale du Génie de l'Eau et de l'Environnement de Strasbourg (ENGEES)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Matériaux et nanosciences d'Alsace (FMNGE), and Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Argon, Exciton, Relaxation (NMR), General Physics and Astronomy, chemistry.chemical_element, 02 engineering and technology, Trapping, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Molecular physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, X-ray photoelectron spectroscopy, chemistry, Excited state, Cluster (physics), Physical and Theoretical Chemistry, 0210 nano-technology, Excitation
Abstract

International audience; The present work combines time-resolved photoelectron spectroscopy on isolated species with high-level data processing to address an issue which usually pertains to materials science: the electronic relaxation dynamics towards the formation of a self-trapped exciton (STE). Such excitons are common excited states in ionic crystals, silica and rare gas matrices. They are associated with a strong local deformation of the matrix. Argon clusters were taken as a model. They are excited initially to a Wannier exciton at 14 eV and their evolution towards the formation of an STE has showed an unusual type of vibronic relaxation where the electronic excitation of the cluster decreases linearly as a function of time with a 0.59 ± 0.06 eV ps−1 rate. The decay was followed for 3.0 ps, and the STE formation occurred in ∼5.1 ± 0.7 ps.

Published
2018

9. Correcting the record: the dimers and trimers of trans-N-methylacetamide

Author

Hannes C. Gottschalk, Michel Mons, Beppo Hartwig, Thomas Forsting, Martin A. Suhm, Institut für Physikalische Chemie [Göttingen], Georg-August-University [Göttingen], Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Structures BioMoléculaires (SBM), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), and Georg-August-University = Georg-August-Universität Göttingen

Subjects
Quantitative Biology::Biomolecules, 010304 chemical physics, Hydrogen bond, Infrared, Dimer, General Physics and Astronomy, Infrared spectroscopy, Trimer, rans-N-methylacetamide, 010402 general chemistry, 01 natural sciences, London dispersion force, Molecular physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, symbols.namesake, chemistry, Computational chemistry, 0103 physical sciences, symbols, Physical and Theoretical Chemistry, Spectroscopy, Raman spectroscopy
Abstract

International audience; The dimer of trans-N-methylacetamide serves as a simple model for hydrogen bonds in peptides, free of any backbone distortions. Its preferred structures represent benchmark systems for an accurate quantum chemical description of protein interactions. The trimer allows for either two linear or three strained hydrogen bonds, with the former being the only structural motif considered so far in the literature, but the latter winning in energy by a large margin due to London dispersion. A combination of linear Raman and infrared supersonic jet techniques with B3LYP-D3/aug-cc-pVTZ quantum chemical predictions corrects earlier tentative spectroscopic assignments based on a hybrid density functional without dispersion correction. Linear Amide I–III infrared spectra of the jet-cooled monomer are compared to those recently obtained by action spectroscopy.

Published
2017

10. Large amplitude motion of the acetylene molecule within acetylene-neon complexes hosted in helium droplets

Author

Jean-Michel Mestdagh, Marc-André Gaveau, M. Briant, Benoît Soep, P. de Pujo, E. Mengesha, Lionel Poisson, Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Dynamique Réactionnelle (DyR), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), and Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010304 chemical physics, General Physics and Astronomy, chemistry.chemical_element, Resonance, 010402 general chemistry, Rotation, 01 natural sciences, Spectral line, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Neon, Acetylene, chemistry, Physics::Plasma Physics, 0103 physical sciences, Astrophysics::Solar and Stellar Astrophysics, Astrophysics::Earth and Planetary Astrophysics, Physical and Theoretical Chemistry, Atomic physics, Spectroscopy, Helium, Superfluid helium-4
Abstract

International audience; Superfluid helium droplets provide an ideal environment for spectroscopic studies with rotational resolution. Nevertheless, the molecular rotation is hindered because the embedded molecules are surrounded by a non-superfluid component. The present work explores the dynamical role of this component in the hindered rotation of C2H2 within the C2H2–Ne complex. A HENDI experiment was built and near-infrared spectroscopy of C2H2–Ne and C2H2 was performed in the spectral region overlapping the ν3/ν2 + ν4 + ν5 Fermi-type resonance of C2H2. The comparison between measured and simulated spectra helped to address the above issue.

Published
2016

11. Determination of accurate electron chiral asymmetries in fenchone and camphor in the VUV range: sensitivity to isomerism and enantiomeric purity

Author

Uwe J. Meierhenrich, Gustavo A. Garcia, Ivan Powis, Iuliia Myrgorodska, Vincent Wanie, Romain Géneaux, Samuel Beaulieu, Lipsa Nag, Valérie Blanchet, Laurent Nahon, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut de Chimie de Nice (ICN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA)-Université Nice Sophia Antipolis (... - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA), Centre d'Etudes Lasers Intenses et Applications (CELIA), Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Bordeaux (UB), Attophysique (ATTO), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interactions, Dynamiques et Lasers (ex SPAM) (LIDyl), Université Paris-Saclay-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS), School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK., School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, UK. Code (UMR, EA, ...), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université Nice Sophia Antipolis (1965 - 2019) (UNS), COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-COMUE Université Côte d'Azur (2015-2019) (COMUE UCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Côte d'Azur (UCA), and Université de Bordeaux (UB)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)

Subjects
[PHYS]Physics [physics], Spectrometer, Chemistry, Analytical chemistry, General Physics and Astronomy, Synchrotron radiation, Photoionization, Electron, Photoelectric effect, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Ion, 0103 physical sciences, Physical and Theoretical Chemistry, Enantiomer, 010306 general physics, Enantiomeric excess
Abstract

International audience; Photoelectron circular dichroism (PECD) manifests itself as an intense forward/backward asymmetry in the angular distribution of photoelectrons produced from randomly-oriented enantiomers by photoionization with circularly-polarized light (CPL). As a sensitive probe of both photoionization dynamics and of the chiral molecular potential, PECD attracts much interest especially with the recent performance of related experiments with visible and VUV laser sources. Here we report, by use of quasi-perfect CPL VUV synchrotron radiation and using a double imaging photoelectron/photoion coincidence (i2PEPICO) spectrometer, new and very accurate values of the corresponding asymmetries on showcase chiral isomers: camphor and fenchone. These data have additionally been normalized to the absolute enantiopurity of the sample as measured by a chromatographic technique. They can therefore be used as benchmarking data for new PECD experiments, as well as for theoretical models. In particular we found, especially for the outermost orbital of both molecules, a good agreement with CMS-Xα PECD modeling over the whole VUV range. We also report a spectacular sensitivity of PECD to isomerism for slow electrons, showing large and opposite asymmetries when comparing R-camphor to R-fenchone (respectively −10% and +16% around 10 eV). In the course of this study, we could also assess the analytical potential of PECD. Indeed, the accuracy of the data we provide are such that limited departure from perfect enantiopurity in the sample we purchased could be detected and estimated in excellent agreement with the analysis performed in parallel via a chromatographic technique, establishing a new standard of accuracy, in the ±1% range, for enantiomeric excess measurement via PECD. The i2PEPICO technique allows correlating PECD measurements to specific parent ion masses, which would allow its application to analysis of complex mixtures

Published
2016

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