Résumé: We present a wave packet propagation-based method to study the electron dynamics in molecular species in the gas phase and adsorbed on metal surfaces. It is a very general method that can be employed to any system where the electron dynamics is dominated by an active electron and the coupling between the discrete and continuum electronic states is of importance. As an example, one can consider resonant molecule–surface electron transfer or molecular photoionization. Our approach is based on a computational strategy allowing incorporating ab initio inputs from quantum chemistry methods, such as density functional theory, Hartree–Fock, and coupled cluster. Thus, the electronic structure of the molecule is fully taken into account. The electron wave function is represented on a three-dimensional grid in spatial coordinates, and its temporal evolution is obtained from the solution of the time-dependent Schrödinger equation. We illustrate our method with an example of the electron dynamics of anionic states localized on organic molecules adsorbed on metal surfaces. In particular, we study resonant charge transfer from the π* orbitals of three vinyl derivatives (acrylamide, acrylonitrile, and acrolein) adsorbed on a Cu(100) surface. Electron transfer between these lowest unoccupied molecular orbitals and the metal surface is extremely fast, leading to a decay of the population of the molecular anion on the femtosecond timescale. We detail how to analyze the time-dependent electronic wave function in order to obtain the relevant information on the system: the energies and lifetimes of the molecule-localized quasistationary states, their resonant wavefunctions, and the population decay channels. In particular, we demonstrate the effect of the electronic structure of the substrate on the energy and momentum distribution of the hot electrons injected into the metal by the decaying molecular resonance.

Résumé: Ultrafast electron transfer between adsorbed organic molecules and metal substrates is studied. In particular, the dynamics of the active electron in the nitroethylene anion/metal-copper surface system has been followed in real time using a wave packet propagation approach, allowing an intuitive analysis of the decay of molecule-localized electronic resonances. We find that the strong coupling with the metal substrate leads to an extremely short lifetime (fs) of the molecular resonance. Comparison between the free-electron metal, Cu(100), and Cu(111) surfaces demonstrates that the electronic band structure of the substrate and the shape of the decaying molecular orbital lead to a highly marked anisotropy of the metal continuum states populated by resonant electron transfer from the adsorbate. This finding points at possible anisotropy effects in adsorbate-adsorbate interactions and it is of particular importance in molecular self assembly at metal surfaces, thus opening the way to a rational design of hybrid metal/organic interfaces with tailored electronic properties.

Résumé: The real-time dynamics of DABCO-argon clusters is investigated in a femtosecond pump-probe experiment where the pump excites DABCO to the S1 state within the argon cluster. The probe operates by photoionization and documents the energy and angular distributions of the resulting photoelectrons. The present work complements a previous work from our group [Awali Phys. Chem. Chem. Phys., 2014, 16, 516-526] where this dynamics was probed at short time, up to 4 ps after the pump pulse. Here, the dynamics is followed up to 500 ps. A multiscale dynamics is observed. It includes a jump between two solvation sites (time scale 0.27 ps) followed by the relaxation of the solvation cage excess vibrational energy (time scale 14 ps) and then by that of DABCO (time scale >150 ps). Polarization anisotropy, double polarization, and angular anisotropy effects are reported also. They are interpreted (quantitatively for the former effect) in terms of decoherence of rotational alignment, driven by the overall rotation of the DABCO-argon clusters. A tomographic view of the DABCO excited orbital, provided by the double anisotropy effect, is discussed on a qualitative basis.

Résumé: Context. Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. This Paper I focuses on the case of X-ray photodesorption from pure methanol ices.
Aims. We aim at experimentally measuring X-ray photodesorption yields (in molecule desorbed per incident photon, displayed as molecule/photon for more simplicity) of methanol and its photo-products from pure CH3OH ices, and to shed light on the mechanisms responsible for the desorption process.
Methods. We irradiated methanol ices at 15 K with X-rays in the 525–570 eV range from the SEXTANTS beam line of the SOLEIL synchrotron facility. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived.
Results. Under our experimental conditions, the CH3OH X-ray photodesorption yield from pure methanol ice is ~10−2 molecule/photon at 564 eV. Photo-products such as CH4, H2CO, H2O, CO2, and CO also desorb at increasing efficiency. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is also detected. The physical mechanisms at play are discussed and must likely involve the thermalization of Auger electrons in the ice, thus indicating that its composition plays an important role. Finally, we provide desorption yields applicable to protoplanetary disk environments for astrochemical models.
Conclusions. The X-rays are shown to be a potential candidate to explain gas-phase abundances of methanol in disks. However, more relevant desorption yields derived from experiments on mixed ices are mandatory to properly support the role played by X-rays in nonthermal desorption of methanol (see Paper II).

Résumé: Five rovibrational bands of the Kr–H2O complex have been recorded in the ν2 bending region of H2O using a quantum cascade laser coupled to a pulsed slit supersonic jet. Four of them have been unambiguously assigned to the Σ and Π states in v2=1,111,110, and 212 rotational levels of the monomer based on ground state combination differences and similarities with the vibration–rotation tunneling states of Ar–H2O. One of the bands is tentatively assigned to a combination band with two quanta of intermolecular van der Waals stretching mode (νs). Due to the efficient rovibrational cooling in our pulsed supersonic expansion, all observed bands originate from the lowest lying states. Four of them are from the lowest ortho ground state Σe(101) and one of them is from the lowest para ground state Σe(000). The jet-cooled spectra have been analyzed in terms of a nearly free internal rotor model taking into account Coriolis couplings between close lying Σ and Π levels. Molecular parameters for the five upper vibrational states, band origin, rotational and centrifugal distortion constants have been accurately determined. The β parameter describing the Coriolis coupling between the Σ and Π states originating from the (212) state has also been obtained.

Résumé: Two-dimensional (2D) chalcogen-based layers will be among the next generation of materials for potential high-tech applications. We present the structural and electronic properties of Tellurium (Te) deposited on the Au(111) surface by high temperature vapor deposition in UHV. We discuss the possible scenarios for the formation of 2D layers ; either AuTe2 metal dichalcogenide, or Au–Te alloy or a single Tellurene layer. Low energy electron diffraction (LEED) and scanning tunneling microscopy (STM) show the existence of several surface reconstructions depending on the Te film thickness in the sub-monolayer regime. We observe the survival of the well-known spin-split Shockley state of the Au(111) surface after Te deposition. The state is shifted to higher binding energy, suggesting a charge transfer at the interface. For 0.33 ML Te, new dispersive bands in the angle-resolved photoemission (ARPES), are due to the strong hybridization between the electronic states of Te and Au. The low intensity and back-folding at the boundaries of the reduced surface Brillouin zone (R-SBZ), prove that these electronic bands represent a naturel 2D electron gas, strongly disturbed by the surface reconstruction. This indicates the fromation of a surface Au–Te alloy. At 0.5 ML Te, a rich, thickness-dependent transition develops from the surface alloy to Tellurene-like structure which excludes the growth of AuTe2 monolayer. Both the surface alloy and the Tellurene monolayer are semiconducting with an occupied-state gap of 0.65 eV.

Résumé: Catechol is an oxygenated aromatic volatile organic compound and a biogenic precursor of secondary organic aerosols. Monitoring this compound in the gas phase is desirable due to its appreciable reactivity with tropospheric ozone. From a molecular point of view, this molecule is attractive since the two adjacent hydroxy groups can interchangeably act as donor and acceptor in an intramolecular hydrogen bonding due to the tunnelling between two symmetrically equivalent structures. Using synchrotron radiation, we recorded a rotationally-resolved Fourier Transform far-infrared (IR) spectrum of the torsional modes of the free and bonded -OH groups forming the intramolecular hydrogen bond. Additionally, the room temperature, pure rotational spectrum was measured in the 70–220 GHz
frequency range using a millimeter-wave spectrometer. The assignment of these molecular transitions was assisted by anharmonic high-level quantum-chemical calculations. In particular, pure rotational lines belonging to the ground and the four lowest energy, vibrationally excited states were assigned. Splitting due to the tunnelling was resolved for the free -OH torsional state. A global fit combining the far-IR and millimeter-wave data provided the spectroscopic parameters of the low-energy far-IR modes, in particular those characterizing the intramolecular hydrogen bond dynamics.

Résumé: Electronic spectra are measured for mass-selected C^+{2????}(n = 6–14) clusters over the visible and near-infrared spectral range through resonance enhanced photodissociation of clusters tagged with N2 molecules in a cryogenic ion trap. The carbon cluster cations are generated through laser ablation of a graphite disk and can be selected according to their collision cross section with He buffer gas and their mass prior to being trapped and spectroscopically probed. The data suggest that the C^+{2????}(n = 6–14) clusters have monocyclic structures with bicyclic structures becoming more prevalent for C^+{22} and larger clusters. The C^+{2????} electronic spectra are dominated by an origin transition that shifts linearly to a longer wavelength with the number of carbon atoms and associated progressions involving excitation of ring deformation vibrational modes. Bands for C^+{12}, C^+{16}, C^+{20}, C^+{24}, and C^+{28} are relatively broad, possibly due to rapid non-radiative decay from the excited state, whereas bands for C^+{14}, C^+{18}, C^+{22}, and C^+_{26} are narrower, consistent with slower non-radiative deactivation.

Résumé: Because of their high stability, the presence of diamond-type molecules has long been suspected in the interstellar medium, a hypothesis supported by the extraction of diamond nanocrystal from some meteorites. We report the rotational and vibrational investigation of two polar derivatives of adamantane (C10H16), 1-cyanoadamantane (C10H15–CN) and 1-isocyanoadamantane (C10H15–NC), using room temperature gas phase absorption spectroscopy. Pure rotational spectra have been recorded at millimeter wavelengths (75–220 GHz) while vibrational spectra were obtained in the far- and mid-infrared domains (50–3500 cm−1). Quantum chemical calculations have been performed on these two C3v rotors to support the spectral analysis enabling the assignment, for both species, of more than 7000 pure rotational transitions in the ground (A1 symmetry) and first vibrationally excited (E symmetry) states, and of most of the infrared active bands. The pure rotational lines were fit to their experimental accuracy using a symmetric-top Hamiltonian. Our study provides all necessary information for an active search of these species in space.

Résumé: New transitions are reported in the submillimeter wave, terahertz, and far-infrared rotation-torsion spectrum of doubly-deuterated methanol CD2HOH. The newly assigned transitions allow us to spectroscopically characterize torsional states with 0⩽K⩽12 and 0⩽vt⩽2. Three line position analyses are carried out. In the first one, restricted to rotation-torsion lines involving torsional states with 3⩽K⩽12 and vt⩽2, rotational energies are evaluated with a J(J+1) Taylor-type expansion for each torsional state. 4853transitions were accounted for with a unitless standard deviation of 11.4. In the second analysis, 126torsional subband centers are fitted to obtain refined torsional parameters including the hindering potential. In the third analysis, 5911rotation-torsion transitions involving torsional states with vt⩽2, and J⩽26 are reproduced with a unitless standard deviation of 3.2 using a four-dimensional rotation-torsion fitting Hamiltonian.

Résumé: We report the observation of a nontrivial spin texture in Dirac node arcs, i.e., novel topological objects formed when Dirac cones of massless particles extend along an open one-dimensional line in momentum space. We find that such states are present in all the compounds of the tetradymite M2Te2X family (M=Ti, Zr, or Hf and X=P or As) regardless of the weak or strong character of the topological invariant. The Dirac node arcs in tetradymites are thus the simplest possible textbook example of a type-I Dirac system with a single spin-polarized node arc.

Résumé: Hydrocarbons such as methane and ethane are present in many solar system objects, including comets, moons and planets. The interaction of these hydrocarbons with water ice at low temperatures could lead to the formation of inclusion compounds, such as clathrate hydrates (water based host cages trapping guest molecules), modifying their retention, stability and therefore evolution. The occurrence of clathrate hydrates on solar system surfaces could be established by remote sensing of their spectroscopic signatures. In this study, we measure and analyse ethane clathrate hydrate spectra recorded in the temperature range from 5.3 to 160 K, covering most of the temperature range of interest for solar system objects. Specific infrared band signatures are identified for the ethane encaged guest. We provide evidence that ethane clathrate hydrate outcrops can be detected by remote sensing on the surface of planetary bodies.

Résumé: Grazing incidence fast atom diffraction (GIFAD) at surfaces has made rapid progress and has established itself as a surface analysis tool where effective energy E perpendicular of the motion towards the surface is in the same range as that in thermal energy atom scattering (TEAS). To better compare the properties of both techniques, we use the diffraction patterns of helium and neon atoms impinging on a LiF (001) surface as a model system. E-Scan, theta-scan, and phi-scan are presented where the primary beam energy E is varied between a few hundred eV up to five keV, the angle of incidence theta between 0.2 and 2 degrees and the azimuthal angle phi around 360 degrees . The resulting diffraction charts are analyzed in terms of high and low values of effective energy E perpendicular. The former provides high resolution at the positions of the surface atoms and the attached repulsive interaction potentials while the second is sensitive to the attractive forces towards the surface. The recent progress of inelastic diffraction is briefly presented.

Résumé: The high resolution vibrational spectrum of ethyl cyanide (C2H5CN) has been investigated in the far-IR using synchrotron-based Fourier transform spectroscopy. The assignment was performed using the Automated Spectral Assignment Procedure (ASAP) allowing accurate rotational energy levels of the four lowest fundamental vibrations of the species, namely the v13=1 @ 205.934099(8)cm−1, v21=1 @ 212.141101(8)cm−1, v20=1 @ 372.635293(15)cm−1, and v12=1 @ 532.699617(16)cm−1 states, to be determined. The analysis not only confirms the applicability of the ASAP in the treatment of (dense) high-resolution infrared spectra but also reveals some of its limitations. Complementary to the infrared study, the pure rotational spectrum of C2H5CN was also studied in selected frequency ranges from 75 to 255GHz. New observations of a prototypical high-mass star-forming region, G327.3–0.6, performed with the Atacama Large Millimeter Array show that vibrational satellites of C2H5CN can be very intense, of order several tens of Kelvin in units of brightness temperature.

Résumé: In matter, any spontaneous symmetry breaking induces a phase transition characterized by an order parameter, such as the magnetization vector in ferromagnets, or a macroscopic many-electron wave function in superconductors. Phase transitions with unknown order parameter are rare but extremely appealing, as they may lead to novel physics. An emblematic and still unsolved example is the transition of the heavy fermion compound [Formula: see text] (URS) into the so-called hidden-order (HO) phase when the temperature drops below [Formula: see text] K. Here, we show that the interaction between the heavy fermion and the conduction band states near the Fermi level has a key role in the emergence of the HO phase. Using angle-resolved photoemission spectroscopy, we find that while the Fermi surfaces of the HO and of a neighboring antiferromagnetic (AFM) phase of well-defined order parameter have the same topography, they differ in the size of some, but not all, of their electron pockets. Such a nonrigid change of the electronic structure indicates that a change in the interaction strength between states near the Fermi level is a crucial ingredient for the HO to AFM phase transition.

Résumé: Enol forms of trifluoroacetylacetone (TFacac) isolated in molecular and rare gas matrices were studied using infrared (IR) and Raman spectroscopy. Additionally, calculations using DFT B3LYP and M06-2X as well as MP2 methods were performed in order to investigate the possibility of coexistence of more than one stable enol form isomer of TFacac. Calculations predict that both stable enol isomers of TFacac, 1,1,1-trifluoro-4-hydroxy-3-penten-2-one (1) and 5,5,5-trifluoro-4-hydroxy-3-penten-2-one (2), could coexist, especially in matrices where the room temperature population is frozen, 1 being the most stable one. Raman and IR spectra of TFacac isolated in nitrogen (N2) and carbon monoxide (CO) matrices exhibit clear absorption bands, which cannot be attributed to this single isomer. Their relative band positions and intensity profiles match well with the theoretical calculations of 2. This allows us to confirm that in N2 and CO matrices both isomers exist in similar amounts. Careful examination of the spectra of TFacac in argon, xenon, neon, normal, and para-hydrogen (Ar, Xe, Ne, nH2, and pH2 respectively) matrices revealed that both isomers coexist in all the explored matrices, whereas 2 was not considered in the previous spectroscopic works. The amount of the second isomer (2) in the as-deposited samples depends on the host. The analysis of TFacac spectra in the different hosts and under various experimental conditions allows the vibrational characterization of both chelated isomers. The comparison with theoretical predictions is also investigated.

Résumé: Six-membered-diaza ring of cinnoline has been fused on naphthalimide dye to give a donor–acceptor system called CinNapht. This red shifted fluorophore, that can be synthesised in gram scale, exhibits a large Stoke shift and a fluorescence quantum yield up to 0.33. It is also characterized by a strong solvatochromic effect from green to red emission as well and can be used for bio-imaging.

Résumé: VUV photoionization dynamics of the S2 molecule were re-investigated from threshold up to 15.0 eV, using synchrotron radiation coupled with double imaging photoelectron/photoion coincidence featuring high resolution capabilities. We measured the first threshold photoelectron spectrum of S2 achieving higher resolution than previous literature to derive accurate spectroscopic constants for a few electronic states of the cation including the X2ΠΩg ground state and the a4Πu, b4Σg–, and B2Σg– states. We also recorded the total ion yield for S2 up to a photon energy of 15.0 eV which, combined with the threshold photoelectron spectrum, led to the assignment of various autoionizing Rydberg series.

Résumé: We introduce a new theoretical formalism to compute solid-state vibrational circular dichroism (VCD) spectra from molecular dynamics simulations. Having solved the origin-dependence problem of the periodic magnetic gauge, we present IR and VCD spectra of (1S,2S)-trans-1,2-cyclohexanediol obtained from first-principles molecular dynamics calculations and nuclear velocity perturbation theory, along with the experimental results. Because the structure model imposes periodic boundary conditions, the common origin of the rotational strength has hitherto been ill-defined and was approximated by means of averaging multiple origins. The new formalism reconnects the periodic model with the finite physical system and restores gauge freedom. It nevertheless fully accounts for nonlocal spatial couplings from the gauge transport term. We show that even for small simulation cells the rich nature of solid-state VCD spectra found in experiments can be reproduced to a very satisfactory level.

Résumé: Context. Carbon is one of the most abundant components in the Universe. While silicates have been the main focus of solid phase studies in protoplanetary discs (PPDs), little is known about the solid carbon content especially in the planet-forming regions (~0.1–10 au). Fortunately, several refractory carbonaceous species present C-H bonds (such as hydrogenated nano-diamond and amorphous carbon as well as polycyclic aromatic hydrocarbons), which generate infrared (IR) features that can be used to trace the solid carbon reservoirs. The new mid-IR instrument MATISSE, installed at the Very Large Telescope Interferometer (VLTI), can spatially resolve the inner regions (~1–10 au) of PPDs and locate, down to the au-scale, the emission coming from carbon grains.
Aims. Our aim is to provide a consistent view on the radial structure, down to the au-scale, as well as basic physical properties and the nature of the material responsible for the IR continuum emission in the inner disk region around HD 179218.
Methods. We implemented a temperature-gradient model to interpret the disk IR continuum emission, based on a multiwavelength dataset comprising a broadband spectral energy distribution and VLTI H-, L-, and N-bands interferometric data obtained in low spectral resolution. Then, we added a ring-like component, representing the carbonaceous L-band features-emitting region, to assess its detectability in future higher spectral resolution observations employing mid-IR interferometry.
Results. Our temperature-gradient model can consistently reproduce our dataset. We confirmed a spatially extended inner 10 au emission in H- and L-bands, with a homogeneously high temperature (~1700 K), which we associate with the presence of stochastically heated nano-grains. On the other hand, the N-band emitting region presents a ring-like geometry that starts at about 10 au with a temperature of 400 K. Moreover, the existing low resolution MATISSE data exclude the presence of aromatic carbon grains (i.e., producing the 3.3 μm feature) in close proximity tothe star (≲1 au). Future medium spectral resolution MATISSE data will confirm their presence at larger distances.
Conclusions. Our best-fit model demonstrates the presence of two separated dust populations: nano-grains that dominate the near- to mid-IR emission in the inner 10 au region and larger grains that dominate the emission outward. The presence of such nano-grains in the highly irradiated inner 10 au region of HD 179218 requires a replenishment process. Considering the expected lifetime of carbon nano-grains from The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS model), the estimated disk accretion inflow of HD 179218 could significantly contribute to feed the inner 10 au region in nano-grains.Moreover, we also expect a local regeneration of those nano-grains by the photo-fragmentation of larger aggregates.

Résumé: Recently developed, nanoscale metal-organic frameworks (nanoMOFs) functionalized with versatile coatings are drawing special attention in the nanomedicine field. Here we show the preparation of core-shell MIL-100(Al) nanoMOFs for the delivery of the anticancer drug doxorubicin (DOX). DOX was efficiently incorporated in the MOFs and was released in a progressive manner, depending on the initial loading. Besides, the coatings were made of biodegradable gamma-cyclodextrin-citrate oligomers (CD-CO) with affinity for both DOX and the MOF cores. DOX was incorporated and released faster due to its affinity for the coating material. A set of complementary solid state nuclear magnetic resonance (ssNMR) experiments including (1)H-(1)H and (13)C-(27)Al two-dimensional NMR, was used to gain a deep understanding on the multiple interactions involved in the MIL-100(Al) core-shell system. To do so, (13)C-labelled shells were synthesized. This study paves the way towards a methodology to assess the nanoMOF component localization at a molecular scale and to investigate the nanoMOF physicochemical properties, which play a main role on their biological applications.

Résumé: ABSTRACT
Line coupling and line mixing effects of CH3Cl lines in the ν1 band perturbed by N2 have been investigated. We have taken into account the non-diagonality of the exp(−S2) operator within specified line spaces as well as the k-degeneracy of the transitions (due to the double degeneracy of the j,k levels with k ≠ 0). These transitions should be considered as doublets coupled by the line mixing process. A new problem appears in the calculation when the atom-atom potential model is introduced. In order to overcome this difficulty, a pragmatic approach is proposed. Comparisons of theoretically calculated matrix elements of W with measurements of QR(j,k) doublets as well as some QQk sub-branches, which are strongly affected by line mixing, have been made. The results show that the formalism improved in this way leads to rather accurate predictions.

Résumé: Non-uniform illumination limits quantitative analyses of fluorescence imaging techniques. In particular, single molecule localization microscopy (SMLM) relies on high irradiances, but conventional Gaussian-shaped laser illumination restricts the usable field of view to around 40 microm x 40 microm. We present Adaptable Scanning for Tunable Excitation Regions (ASTER), a versatile illumination technique that generates uniform and adaptable illumination. ASTER is also highly compatible with optical sectioning techniques such as total internal reflection fluorescence (TIRF). For SMLM, ASTER delivers homogeneous blinking kinetics at reasonable laser power over fields-of-view up to 200 microm x 200 microm. We demonstrate that ASTER improves clustering analysis and nanoscopic size measurements by imaging nanorulers, microtubules and clathrin-coated pits in COS-7 cells, and beta2-spectrin in neurons. ASTER's sharp and quantitative illumination paves the way for high-throughput quantification of biological structures and processes in classical and super-resolution fluorescence microscopies.

Résumé: Spectra of CO2+H2 mixtures have been recorded at room temperature by using the cavity ring down technique, for four spectral intervals in the 2.12-2.35 µm CO2 spectral window which is within the (1-0) band of H2. The binary coefficients BCO2−H2+BH2−CO2have been retrieved from the spectra recorded at different pressures after subtraction of the CO2 monomer contribution and of the H2-H2 and CO2-CO2 collision induced absorptions (CIAs). In order to reduce the uncertainties, new measurement of the pure H2 CIA, the main subtracted contribution, at the percent level are also reported. The new set of experimental binary coefficients is compared to values provided by semi-empirical calculations made with the assumption of an isotropic CO2-H2 interaction potential and neglecting the short interaction-range induced electric dipole. This comparison shows the limits of using such a model, which is the only one available, in that spectral region.

Résumé: Elastic diffraction of fast atoms at crystal surfaces under grazing incidence θ ≈ 1° has strong similarities with atomic diffraction at thermal energies discovered almost hundred years ago. Here, we focus on the polar scattering profile, which does not exhibit diffraction features but shows well-defined elastic and inelastic components that are found to be essentially independent of the crystallographic axis. The width σθ of the inelastic component is very sensitive to the weak attractive forces responsible for the physisorption. This effect is visible on an energy range almost ten times larger than the depth D of the physisorption well. Experimental data are analyzed using a binary collision model with a Morse potential where the width σθ of the scattering profile is connected to the classical energy loss and is governed by the surface stiffness, defined as the logarithmic derivative of the interaction potential along the surface normal. The main outcome is that the weak attractive forces make the mean surface potential almost twice harder at low energy.

Résumé: The protonated cyclo (LTyr-LPro) and cyclo (LTyr-DPro) dipeptides based on a diketopiperazine (DKP) ring are studied by tandem mass spectrometry in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. Collision-induced dissociation (CID) and infrared multiple-photon dissociation (IRMPD) spectroscopy results are interpreted with the aid of quantum chemical calculations and chemical dynamics simulations. All the conformers identified for each diastereomer, denoted c-LLH+ and c-LDH+, respectively, are protonated on the carbonyl group of the tyrosine. The most stable form has an extended structure with the aromatic ring oriented outside the DKP ring; it is stabilized by an OH+…π interaction. Distinct IR signatures are obtained for the extended conformers of c-LLH+ and c-LDH+, which differ by the strength of the OH+…π interaction, much stronger in c-LLH+. Less stable species with the aromatic ring folded over the DKP ring are kinetically trapped in our experimental conditions, but their IR spectrum is identical for c-LLH+ and c-LDH+. The main collision-induced dissociation products of the protonated dipeptides are analyzed using chemical dynamics simulations. More efficient CID is observed for c-LDH+, in particular for the formation of the iminium ion of tyrosine. In contrast to the monomers, the protonated dimers of c-LLH+ and c-LDH+ show identical IR spectra. This is explained in terms of a structure involving a single strong OH+…O interaction between subunits not sensitive to the absolute configuration of the residues, i.e., from a folded protonated monomer to an extended neutral monomer.

Résumé: Glyoxylic and pyruvic oxoacids are widely available in the atmosphere as gas-phase clusters and particles or in wet aerosols. In aqueous conditions, they undergo interconversion between the unhydrated oxo and gem-diol forms, where two hydroxyl groups replace the carbonyl group. We here examine the hydration equilibrium of glyoxylic and pyruvic acids with first-principles simulations in water at ambient conditions using ab initio metadynamics to reconstruct the corresponding free-energy landscapes. The main results are as follows: (i) our simulations reveal the high conformational diversity of these species in aqueous solutions. (ii) We show that gem-diol is strongly favored in water compared to its oxo counterpart by 29 and 16 kJ/mol for glyoxylic and pyruvic acids, respectively. (iii) From our atomic-scale simulations, we present new insights into the reaction mechanisms with a special focus on hydrogen-bond arrangements and the electronic structure of the transition state.

Résumé: Silicene, a new 2D material has attracted intense research because of the
ubiquitous use of silicon in modern technology. However, producing freestanding
silicene has proved to be a huge challenge. Until now, silicene could be synthesized only on metal surfaces where it naturally forms strong interactions with the metal substrate that modify its electronic properties. Here, the authors report the first experimental evidence of silicene sheet on an insulating NaCl thin film. This work represents a major breakthrough, for the study of the intrinsic properties of silicene, and by extension to other 2D materials that have so far only been grown on metal surfaces.

Résumé: The annual flux of extraterrestrial material on Earth is largely dominated by sub-millimetre particles. The mass distribution and absolute value of this cosmic dust flux at the Earth's surface is however still uncertain due to the difficulty in monitoring both the collection efficiency and the exposure parameter (i.e. the area-time product in m2.yr). In this paper, we present results from micrometeorite collections originating from the vicinity of the CONCORDIA Station located at Dome C (Antarctica), where we performed several independent melts of large volumes of ultra-clean snow. The regular precipitation rate and the exceptional cleanliness of the snow from central Antarctica allow a unique control on both the exposure parameter and the collection efficiency. A total of 1280 unmelted micrometeorites (uMMs) and 808 cosmic spherules (CSs) with diameters ranging from 30 to 350 μm were identified. Within that size range, we measured mass fluxes of 3.0 μg.m−2.yr−1 for uMMs and 5.6 μg.m−2.yr−1 for CSs. Extrapolated to the global flux of particles in the 12-700 μm diameter range, the mass flux of dust at Earth's surface is 5,200±12001500 tons.yr−1 (1,600±500 and 3,600±7001000 tons.yr−1 of uMMs and CSs, respectively). We indicate the statistical uncertainties expected for collections with exposure parameters in the range of 0.1 up to 105 m2.yr. In addition, we estimated the flux of altered and unaltered carbon carried by heated and un-heated particles at Earth's surface. The mass distributions of CSs and uMMs larger than 100 μm are fairly well reproduced by the CABMOD-ZoDy model that includes melting and evaporation during atmospheric entry of the interplanetary dust flux. These numerical simulations suggest that most of the uMMs and CSs originate from Jupiter family comets and a minor part from the main asteroid belt. The total dust mass input before atmospheric entry is estimated at 15,000 tons.yr−1. The existing discrepancy between the flux data and the model for uMMs below 100 μm suggests that small fragile uMMs may evade present day collections, and/or that the amount of small interplanetary particles at 1 AU may be smaller than expected.

Résumé: An easily synthesized α-hydroxy-β-azidotetrazole scaffold was used to build a three dimensional polychromic system. Different chromophores (coumarin, BODIPY and distyryl BODIPY) were incorporated into the structure by using sequential CuAAC reactions to form a series of dyads and a triad. A computational study of the resulting arrays showed that the predominant conformations brought the substituents into close spatial proximity. The triad exhibited FRET behaviour with notably efficient energy transfer values.

Résumé: The stability of the molecular self-assembled monolayers (SAMs) is of vital importance to the performance of the molecular electronics and their integration to the future electronics devices. Here we study the effect of electron irradiation-induced cross-linking on the stability of self-assembled monolayer of aromatic 5,5'-bis(mercaptomethyl)-2,2'-bipyridine [BPD; HS-CH(2)-(C(5)H(3)N)(2)-CH(2)-SH] on Au (111) single crystal surface. As a refence, we also study the properties of SAMs of electron saturated 1-dodecanethiol [C12; CH(3)-(CH(2))(11)-SH] molecules. The stability of the considered SAMs before and after electron-irradiation is studied using low energy Ar(+) cluster depth profiling monitored by recording the X-ray photoelectron spectroscopy (XPS) core level spectra and the UV-photoelectron spectroscopy (UPS) in the valance band range. The results indicate a stronger mechanical stability of BPD SAMs than the C12 SAMs. The stability of BPD SAMs enhances further after electron irradiation due to intermolecular cross-linking, whereas the electron irradiation results in deterioration of C12 molecules due to the saturated nature of the molecules. The depth profiling time of the cross-linked BPD SAM is more than 4 and 8 times longer than the profiling time obtained for pristine and BPD and C12 SAMs, respectively. The UPS results are supported by density functional theory calculations, which show qualitative agreement with the experiment and enable us to interpret the features in the XPS spectra during the etching process for structural characterization. The obtained results offer helpful options to estimate the structural stability of SAMs which is a key factor for the fabrication of molecular devices.

Résumé: A full-dimensional wavepacket propagation describing the bimolecular exchange reactions H + H'OD --> H'OH + D or HOD + H' initiated by photolysis of HCl in the hydrogen-bound complex (HCl)---(HOD) is reported. The dynamics of this reaction is carried out with the MCTDH method on an ab initio potential energy surface (PES) of H3O and the initial state is derived from the ground state wavefunction of the complex obtained by relaxation on its own electronic ground state ab initio PES. The description of the system makes use of polyspherical coordinates parametrizing a set of Radau and Jacobi vectors. The calculated energy- and time-resolved reaction probabilities show, owing to the large collision energies at play stemming from the (almost full) photolysis of HCl, that the repulsion between oxygen in the H'OD molecule and the incoming hydrogen atom is the main feature of the collision and leads to non-reactive scattering. No abstraction reaction products are observed. However, both exchange processes are still observable, with a preference in O-H' bond dissociation over that of O-D. The selectivity is reversed upon vibrational pre-excitation of the O-D stretching mode in the H'OD molecule. It is shown that, after the collision, the hydrogen atom of HCl does most likely not encounter the almost stationary chlorine atom again but we also consider the limit case where the H atom is forced to collide multiple times against H'OD as a result of being pushed back by the Cl atom.

Résumé: The synthesis of tetraphenylporphyrin erbium(III) acetylacetonate (acac) complexes is realized and their properties studied at the nanoscale when adsorbed on a semi-insulating CaF2/Si(100) surface. Our findings reveal that the ErTPP-(acac) molecules can adsorb in two main on-site conformations. Following precisely located dI/dV measurements at various specific positions [phenyls, pyrroles, and Er-(acac)], the relative locations of the Er cation and the apical ligand (acac) can be deciphered for each observed conformation. Hence, one of the adsorbate conformations presents the acac ligand parallel to the porphyrin plane with the Er atom outside the macrocycle plane. The second conformation is related to what is known in the gas phase, where the acac ligand is oriented vertically on top of the Er atom. This work is combined with a theoretical investigation that uses density functional theory methods to bring into light details of the two observed conformations. Additional proofs of our discoveries are related to the vibrational excitations of ErTPP-(acac). A comparison with a theoretical estimation of the vibrational modes reveals how the electronic resonance near the valence-band edge of the insulting layer is suitable to distinguish between the two adsorbed conformations.

Résumé: A full-dimensional quantum dynamical study for the bimolecular reactions of hydrogen molecules with amino radicals for different isotopologues is reported. The nonreactive amino radical is described by two Radau vectors that are very close to the valence bond coordinates. Potential-optimized discrete variable representation basis is used for the vibrational coordinates of the amino radical. Starting from the reaction H2 + NH2, we study the isotope effects for the two reagents separately, i.e., H2 + NH2/ND2/NHD and H2/D2/HD + NH2. The effects of different vibrational mode excitations of the reagents on the reactivities are studied. Physical explanations about the isotope effects are also provided thoroughly including the influence of vibrational energy differences between the different isotopologues and the impact of the tunneling effect.

Résumé: Blue phosphorene (blue-P) has attracted considerable attention due to its potential applications in optical and electronic devices. However, its synthesis has remained a challenge. Here, we report an experimental investigation of the first steps of blue-P growth on Au(1 1 1) surface by molecular-beam epitaxy. The structure was characterized by in situ low temperature scanning tunneling microscopy, low-energy electron diffraction, combined with density functional theory calculations. We reveal two-dimensional (2D) phosphorus clusters (P-clusters) formed on surface at 150 °C, where the most prevalent structure of P-clusters is composed of triangles with six protrusions. We also demonstrate the transformation of these P-clusters into a single layer of blue-P after post-annealing at 260 °C. Our observation of the growth process is a necessary step for exploring the growth mechanisms further.

Résumé: Focal adhesions (FAs) initiate chemical and mechanical signals involved in cell polarity, migration, proliferation and differentiation. Super-resolution microscopy revealed that FAs are organized at the nanoscale into functional layers from the lower plasma membrane to the upper actin cytoskeleton. Yet, how FAs proteins are guided into specific nano-layers to promote interaction with given targets is unknown. Using single protein tracking, super-resolution microscopy and functional assays, we link the molecular behavior and 3D nanoscale localization of kindlin with its function in integrin activation inside FAs. We show that immobilization of integrins in FAs depends on interaction with kindlin. Unlike talin, kindlin displays free diffusion along the plasma membrane outside and inside FAs. We demonstrate that the kindlin Pleckstrin Homology domain promotes membrane diffusion and localization to the membrane-proximal integrin nano-layer, necessary for kindlin enrichment and function in FAs. Using kindlin-deficient cells, we show that kindlin membrane localization and diffusion are crucial for integrin activation, cell spreading and FAs formation. Thus, kindlin uses a different route than talin to reach and activate integrins, providing a possible molecular basis for their complementarity during integrin activation.

Résumé: Metal-organic frameworks (MOFs), comprised of organic ligands and metal ions/metal clusters via coordinative bonds are highly porous, crystalline materials. Their tunable porosity, chemical composition, size and shape, and easy surface functionalization make this large family more and more popular for drug delivery. There is a growing interest over the last decades in the design of engineered MOFs with controlled sizes for a variety of biomedical applications. This article presents an overall review and perspectives of MOFs-based drug delivery systems (DDSs), starting with the MOFs classification adapted for DDSs based on the types of constituting metals and ligands. Then, the synthesis and characterization of MOFs for DDSs are developed, followed by the drug loading strategies, applications, biopharmaceutics and quality control. Importantly, a variety of representative applications of MOFs are detailed from a point of view of applications in pharmaceutics, diseases therapy and advanced DDSs. In particular, the biopharmaceutics and quality control of MOFs-based DDSs are summarized with critical issues to be addressed. Finally, challenges in MOFs development for DDSs are discussed, such as biostability, biosafety, biopharmaceutics and nomenclature.