Résumé: The intramolecular vibrational relaxation dynamics of formic acid and its deuterated isotopologues is simulated on the full-dimensional potential energy surface of Richter and Carbonniere [J. Chem. Phys. 148, 064303 (2018)] using the Heidelberg MCTDH package. We focus on couplings with the torsion vibrational modes close to the trans-cis isomerization coordinate from the dynamics of artificially excited vibrational mode overtones. The bright C-O stretch vibrational mode is coupled to the out-of-the plane torsion mode in HCOOH, where this coupling could be exploited for laser-induced trans-to-cis isomerization. Strong isotopic effects are observed: deuteration of the hydroxyl group, i.e., in HCOOD and DCOOD, destroys the C-O stretch to torsion mode coupling whereas in DCOOH, little to no effect is observed.

Résumé: The precision of matter-wave sensors benefits from interrogating large-particle-number atomic ensembles at high cycle rates. Quantum-degenerate gases with their low effective temperatures allow for constraining systematic errors towards highest accuracy, but their production by evaporative cooling is costly with regard to both atom number and cycle rate. In this work, we report on the creation of cold matter-waves using a crossed optical dipole trap and shaping them by means of an all-optical matter-wave lens. We demonstrate the trade off between lowering the residual kinetic energy and increasing the atom number by reducing the duration of evaporative cooling and estimate the corresponding performance gain in matter-wave sensors. Our method is implemented using time-averaged optical potentials and hence easily applicable in optical dipole trapping setups.

Résumé: We use time-dependent density functional theory (TDDFT) within the jellium model to study the impact of quantum-mechanical effects on the self-interaction Green’s function that governs the electromagnetic interaction between quantum emitters and plasmonic metallic nanoantennas. A semiclassical model based on the Feibelman parameters, which incorporates quantum surface-response corrections into an otherwise classical description, confirms surface-enabled Landau damping and the spill out of the induced charges as the dominant quantum mechanisms strongly affecting the nanoantenna–emitter interaction. These quantum effects produce a redshift and broadening of plasmonic resonances not present in classical theories that consider a local dielectric response of the metals. We show that the Feibelman approach correctly reproduces the nonlocal surface response obtained by full quantum TDDFT calculations for most nanoantenna–emitter configurations. However, when the emitter is located in very close proximity to the nanoantenna surface, we show that the standard Feibelman approach fails, requiring an implementation that explicitly accounts for the nonlocality of the surface response in the direction parallel to the surface. Our study thus provides a fundamental description of the electromagnetic coupling between plasmonic nanoantennas and quantum emitters at the nanoscale.

Résumé: X-ray photodesorption yields of N215 and CO13 are derived as a function of the incident photon energy near the N ( approximately 400 eV) and O K-edge ( approximately 500 eV) for pure N215 ice and mixed CO13:N215 ices. The photodesorption spectra from the mixed ices reveal an indirect desorption mechanism for which the desorption of N215 and CO13 is triggered by the photoabsorption of CO13 and N215, respectively. This mechanism is confirmed by the x-ray photodesorption of CO13 from a layered CO13/N215 ice irradiated at 401 eV on the N 1s --> pi* transition of N215. This latter experiment enables us to quantify the relevant depth involved in the indirect desorption process, which is found to be 30-40 monolayers in that case. This value is further related to the energy transport of Auger electrons emitted from the photoabsorbing N215 molecules that scatter toward the ice surface, inducing the desorption of CO13. The photodesorption yields corrected from the energy that can participate in the desorption process (expressed in molecules desorbed by eV deposited) do not depend on the photon energy; hence, they depend neither on the photoabsorbing molecule nor on its state after Auger decay. This demonstrates that x-ray induced electron stimulated desorption, mediated by Auger scattering, is the dominant process explaining the desorption of N215 and CO13 from the ices studied in this work.

Résumé: Calculations of the N2-, O2-, and air-broadened widths, together with their temperature dependence exponents have been made for transitions of CH3I in the ν5 and ν6 bands. The calculations are based on a semi-classical line shape formalism developed by the current authors through modifying and refining the Robert-Bonamy formalism. In recent years, we have applied this formalism for linear molecules, symmetric-top molecules with inversion symmetry, and asymmetric-top molecules. For symmetric-top molecules with the k degeneracy such as CH3I, the formalism has a new feature. In this case, one should consider each of the CH3I transitions labeled by ki or f ≠ 0 as a doublet. Then, one needs to consider the effects of the line mixing process between these two components. Comparisons of our theoretical predictions with some data available demonstrate a very reasonable agreement. Finally we propose new experiments at higher perturber pressures that would enable one to check the theoretically calculated relaxation matrices and to extend the analysis to the inter-doublet mixing effects.

Résumé: Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N2 mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N2), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters (Cn+) and polyacetylene cations (HC2nH+) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected Au+2 and Au2Ag+ clusters.

Résumé: The first measurement of the photoelectron spectrum of the silylidyne free radical, SiH, is reported between 7 and 10.5 eV. Two main photoionizing transitions involving the neutral ground state, X+ 1Σ+ ← X 2 Π and a+ 3Π ← X 2 Π, are assigned by using ab initio calculations. The corresponding adiabatic ionization energies are derived, IEad (X+ 1Σ+ ) = 7.934(5) eV and IEad (a+ 3Π) = 10.205(5) eV, in good agreement with our calculated values and the previous determination by Berkowitz et al. [J. Chem. Phys. 86, 1235 (1987)] from a photoionization mass spectrometric study. The photoion yield of SiH recorded in this work exhibits a dense autoionization landscape similar to that observed in the case of the CH free radical [Gans et al., J. Chem. Phys. 144, 204307 (2016)].

Résumé: The (sub-)millimeter wave spectrum of the non-rigid CH2OH radical is investigated both experimentally and theoretically. Ab initio calculations are carried out to quantitatively characterize its potential energy surface as a function of the two large amplitude ∠H1COH and ∠H2COH dihedral angles. It is shown that the radical displays a large amplitude torsional-like motion of its CH2 group with respect to the OH group. The rotation–torsion levels computed with the help of a 4D Hamiltonian accounting for this torsional-like motion and for the overall rotation exhibit a tunneling splitting, in agreement with recent experimental investigations, and a strong rotational dependence of this tunneling splitting on the rotational quantum number Ka due to the rotation–torsion Coriolis coupling. Based on an internal axis method approach, a fitting Hamiltonian accounting for tunneling effects and for the fine and hyperfine structure is built and applied to the fitting of the new (sub)-millimeter wave transitions measured in this work along with previously available high-resolution data. 778 frequencies and wavenumbers are reproduced with a unitless standard deviation of 0.79 using 27 parameters. The N = 0 tunneling splitting, which could not be determined unambiguously in the previous high-resolution investigations, is determined based on its rotational dependence.

Résumé: Context. Interstellar dust grain growth in dense clouds and protoplanetary disks, even when moderate, affects the observed interstellar ice profiles as soon as a significant fraction of dust grains are in the size range close to the wave vector at the considered wavelength. The continuum baseline correction made prior to analysing ice profiles influences the subsequent analysis and hence the estimated ice composition, which are typically obtained by band fitting using thin film ice mixture spectra.
Aims. We explore the effect of grain growth on the spectroscopic profiles of ice mantle constituents, focusing particularly on carbon dioxide, with the aim of understanding how it can affect interstellar ice mantle spectral analysis and interpretation.
Methods. Using the discrete dipole approximation for scattering and absorption of light, the mass absorption coefficients of several distributions of grains – composed of ellipsoidal silicate cores with water and carbon dioxide ice mantles – are calculated. A few models also include amorphous carbon in the core and pure carbon monoxide in the ice mantle. We explore the evolution of the size distribution starting in the dense core phase in order to simulate the first steps of grain growth up to three microns in size. The resulting mass absorption coefficients are injected into RADMC-3D radiative transfer models of spherical dense core and protoplanetary disk templates to retrieve the observable spectral energy distributions. Calculations are performed using the full scattering capabilities of the radiative transfer code. We then focus on the particularly relevant calculated profile of the carbon dioxide ice band at 4.27 µm.
Results. The carbon dioxide anti-symmetric stretching mode profile is a meaningful indicator of grain growth. The observed profiles towards dense cores obtained with the Infrared Space Observatory and Akari satellites already show profiles possibly indicative of moderate grain growth.
Conclusions. The observation of true protoplanetary disks at high inclination with the James Webb Space Telescope should present distorted profiles that will allow constraints to be placed on the extent of dust growth. The more evolved the dust size distribution, the more the extraction of the ice mantle composition will require both understanding and taking grain growth into account.

Résumé: Context. Di-deuterated molecules are observed in the earliest stages of star formation at abundances of a few percent relative to their nondeuterated isotopologs, which is unexpected considering the scarcity of deuterium in the interstellar medium. With sensitive observations leading to the detection of a steadily increasing number of di-deuterated species, it is becoming possible to explore successive deuteration chains.
Aims. The accurate quantification of the column density of di-deuterated methanol is a key piece of the puzzle that is missing in the otherwise thoroughly constrained family of D-bearing methanol in the deeply embedded low-mass protostellar system and astrochemical template source IRAS 16293-2422. A spectroscopic dataset for astrophysical purposes was built for CHD2OH and made publicly available to facilitate the accurate characterization of this species in astrochemical surveys.
Methods. The newly computed line list and partition function were used to search for CHD2OH toward IRAS 16293-2422 A and B in data from the Atacama Large Millimeter/submillimeter Array (ALMA) Protostellar Interferometric Line Survey (PILS). Only nonblended, optically thin lines of CHD2OH were used for the synthetic spectral fitting.
Results. The constructed spectroscopic database contains line frequencies and strengths for 7417 transitions in the 0–500 GHz frequency range. ALMA-PILS observations in the 329–363 GHz range were used to identify 105 unique, nonblended, optically thin line frequencies of CHD2OH for synthetic spectral fitting. The derived excitation temperatures and column densities yield high D/H ratios of CHD2OH in IRAS 16293-2422 A and B of 7.5 ± 1.1% and 7.7 ± 1.2%, respectively.
Conclusions. Deuteration in IRAS 16293-2422 is not higher than in other low-mass star-forming regions (L483, SVS13-A, NGC 1333-IRAS2A, -IRAS4A, and -IRAS4B). Di-deuterated molecules consistently have higher D/H ratios than their mono-deuterated counterparts in all low-mass protostars, which may be a natural consequence of H–D substitution reactions as seen in laboratory experiments. The Solar System’s natal cloud, as traced by comet 67P/Churyumov–Gerasimenko, may have had a lower initial abundance of D, been warmer than the cloud of IRAS 16293-2422, or been partially reprocessed. In combination with accurate spectroscopy, a careful spectral analysis, and the consideration of the underlying assumptions, successive deuteration is a robust window on the physicochemical provenance of star-forming systems.

Résumé: We present computations, solely using input data from the literature and thus free of any adjusted parameter, of the far infrared collision-induced absorption (CIA) by interacting CH4 and CO2 molecules. They are based on classical molecular dynamics simulations (CMDS) of the rotational and translational motions of the molecules made using an accurate ab initio CH4-CO2 anisotropic intermolecular potential, and on a long-range expansion of the interaction-induced dipole. Various desymmetrization procedures, which all ensure detailed balance of the spectral density function are a posteriori applied to the CMDS results. The comparison with the available measurements, which have been collected at room temperature, show that a good agreement can be obtained without introducing any ad hoc short-range dipole components, and it enables to point out the limits of some of the desymmetrization procedures. Tests are also made of the so-called “isotropic approximation”, which point out its strong limits, since it leads to large underestimations of the CIA, and question previous computations made using an isotropic potential and long-range expansion of the induced dipole complemented by ad hoc contributions at short distances. Finally, the temperature dependence of the CIA is predicted for applications to planetary atmospheres.

Résumé: Ultracold quantum gases are ideal sources for high-precision space-borne sensing as proposed for Earth observation, relativistic geodesy and tests of fundamental physical laws as well as for studying new phenomena in many-body physics during extended free fall. Here we report on experiments with the Cold Atom Lab aboard the International Space Station, where we have achieved exquisite control over the quantum state of single (87)Rb Bose-Einstein condensates paving the way for future high-precision measurements. In particular, we have applied fast transport protocols to shuttle the atomic cloud over a millimeter distance with sub-micrometer accuracy and subsequently drastically reduced the total expansion energy to below 100 pK with matter-wave lensing techniques.

Résumé: The spontaneous formation of biological substances, such as human organs, are governed by different stimuli driven by complex 3D self-organization protocols at the molecular level. The fundamentals of such molecular self-assembly processes are critical for fabrication of advanced technological components in nature. We propose and experimentally demonstrate a promising 3D printing method with self-healing property based on molecular self-assembly-monolayer principles, which is conceptually different than the existing 3D printing protocols. The proposed molecular building-block approach uses metal ion-mediated continuous self-assembly of organic molecular at liquid-liquid interfaces to create 2D and 3D structures. Using this technique, we directly printed nanosheets and 3D rods using dithiol molecules as building block units.

Résumé: A new experimental method has been developed to record photoelectron spectra based on the well-established pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy technique and inspired by the data treatment employed in slow photoelectron spectroscopy. This method has been successfully applied to two well-known systems: the X+2Πg, 1/2 (v+=0) ← X 1Σ+g (v=0) and the X+1Σ+ (v+=2) ← X 2Π1/2 (v=0) ionizing transitions of CO2 and NO, respectively. The first results highlight several advantages of our technique such as an improved signal-to-noise ratio without degrading the spectral resolution and a direct field-free energy determination. The data obtained for NO indicate that this method might be useful for studying field-induced autoionization processes.

Résumé: Single-photon multiple photoionization results from electron correlations that make this process possible beyond the independent electron approximation. To study this phenomenon experimentally, the detection in coincidence of all emitted electrons is the most direct approach. It provides the relative contribution of all possible multiple ionization processes, the energy distribution between electrons that can reveal simultaneous or sequential mechanisms, and, if possible, the angular correlations between electrons. In the present work, we present a new magnet design of our magnetic bottle electron spectrometer that allows the detection of multiply charged Xe(n+) ions in coincidence with n electrons. This new coincidence detection allows more efficient extraction of minor channels that are otherwise masked by random coincidences. The proof of principle is provided for xenon triple ionization.

Résumé: Only 4 of the diffuse interstellar bands (DIBs) are currently accounted for, ascribed to electronic transitions of C_{60}^+. Investigations into carriers of other DIBs historically focus on charged and neutral hydrocarbons, and little information is available regarding oxygenated carbon and hydrocarbon species that result from the two most abundant heavy elements in the interstellar medium, C and O. In this study, we assess whether CnO+, HCnO+, and OCnO+ (n = 4 − 9) cations are viable candidates to account for DIBs using both density-functional theory (DFT) and coupled cluster single-double and perturbative triple theory, CCSD(T). For these species, the linear structures are the most stable isomers with the lowest dissociation threshold corresponding to CO loss. Optical absorptions of the oxygenated carbon chain cations are characterized by calculated vertical excitation wavelengths and their corresponding oscillator strengths using the equation-of-motion CCSD (EOM-CCSD) method. Aside from HC4O+ and HC2n + 1O+, all of the species considered in this study have calculated electronic transitions that lie in the visible or near-infrared spectral regions. Minimal column densities necessary for these cations to account for DIBs have been estimated. Based on present results and the known column densities for neutral oxygenated carbon chains in TMC-1, the growth rate of charged O-bearing carbon chains via ion-neutral reaction mechanisms is judged to be too low to form a sufficient population to give rise to DIBs.

Résumé: Context. The recent detection in pre-stellar sources of cyano-substituted and pure hydrocarbon cycles has emphasized the importance of aromatic chemistry in the earliest stages of star formation. Ultraviolet (UV) and vacuum-UV (VUV) radiation is ubiquitous in space and thus the photo-processing of small cyclic ions may open a window onto rich chemical networks and lead to the formation of larger aromatics in space.
Aims. The aim is to investigate the fate of protonated benzonitrile species after UV and VUV photoexcitation and the subsequent potential impact on stellar and interstellar chemistry.
Methods. Protonated benzonitrile was isolated in a linear ion trap prior to irradiation with UV and VUV radiation (4.5–13.6 eV) from the DESIRS beamline at synchrotron SOLEIL. The study was extended down to 3.5 eV using a cryogenic Paul ion trap coupled to an OPO laser at the PIIM laboratory. Photodissociation action spectra were obtained by monitoring the photofragment yields as a function of photon energy.
Results. The UV/VUV photodissociation action spectra of protonated benzonitrile show structured bands from 3.8 to 9 eV. The primary dissociation channel of protonated benzonitrile corresponds to HCN/HNC loss and formation of the phenylium cation (C6H5+); whereas at high energies, a minor channel is observed that correlates with HC3N loss and formation of C4H5+.
Conclusions. The UV and VUV photodestruction of protonated benzonitrile leads to the formation of a highly reactive cationic species, C6H5+, predicted to be an important precursor of larger aromatic molecules in space, such as polycyclic aromatic hydrocarbons. The inclusion of C6H5+ – a precursor of benzene and, by extension, of benzonitrile – as the result of formation via the photodissociation of protonated benzonitrile in current astrochemical models could improve the predicted abundance of benzonitrile, which is currently underestimated.

Résumé: The dynamics of the electronically excited pyruvic acid (PA) and of its unimolecular decomposition upon single photon ionisation are investigated by means of a table top fs laser and VUV synchrotron radiation. The latter is coupled with photo-ion/photo-electron coincidence acquisition devices that allow the identification of the ionic products coming from state-to-state fragmentation upon ionisation. The fs-based setup provides time-resolved mass spectra with 266 nm (= 4.661 eV) excitation and an 800 nm multiphoton probe. For interpretation, we carried out theoretical computations using a composite scheme combining density functional theory full molecular geometric optimisation and post-Hartree-Fock correction inclusion. We therefore determined the neutral and ionic species formed during these experiments and the corresponding dissociation channels. Although several PA isomers are found, we show that solely the most stable isomer of PA (i.e. Tc) is present in the molecular beam prior to ionisation. We determined its adiabatic ionisation energy (AIE = 10.031 +/- 0.005 eV). The fragmentation of the Tc(+) ion occurs at approximately 0.4 eV above the threshold and it is dominated by the CC bond breaking channel, forming the HOCO fragment in conjunction with the CH3CO(+) ion. The decarboxylation of Tc(+) channels has a minor contribution, although they are more favourable thermodynamically. These findings are in contrast with the dominance of decarboxylation while fragmenting Tc populated in the S1-S3 states. For explanation, we invoke an indirect process populating first a short lived autoionising neutral state located in energy at the HOCO + CH3CO(+) dissociation limit. Later on, fragmentation occurs, followed by autoionisation. On the other hand, the fs-based experiment does not reveal any appreciable dynamics for the Tc isomer of PA after a 266 nm excitation because of non-favourable Franck-Condon factors at this energy. In sum, our work highlights the importance of the couplings between the parent ion vibrational modes and the dissociative channels in the vicinity of the loss ionic fragmentation thresholds.

Résumé: The excitation of low-energy electron–hole pairs is one of the most relevant processes in the gas–surface interaction. An efficient tool to account for these excitations in simulations of atomic and molecular dynamics at surfaces is the so-called local density friction approximation (LDFA). The LDFA is based on a strong approximation that simplifies the dynamics of the electronic system: a local friction coefficient is defined using the value of the electronic density for the unperturbed system at each point of the dynamics. In this work, we apply real-time time-dependent density functional theory to the problem of the electronic friction of a negative point charge colliding with spherical jellium metal clusters. Our non-adiabatic, parameter-free results provide a benchmark for the widely used LDFA approximation and allow the discussion of various processes relevant to the electronic response of the system in the presence of the projectile.

Résumé: The protonated dimers of the diketopiperazine dipeptide cyclo (lPhe-lHis) and cyclo (lPhe-dHis) are studied by laser spectroscopy combined with mass spectrometry to shed light on the influence of stereochemistry on the clustering propensity of cyclic dipeptides. The marked spectroscopic differences experimentally observed in the hydride stretch region are well accounted for by the results of DFT calculations. Both diastereomeric protonated dimers involve a strong ionic hydrogen bond from the protonated imidazole ring of one monomer to the neutral imidazole nitrogen of the other. While this strong interaction is accompanied by a single NH⋯O hydrogen bond between the amide functions of the two moieties for the protonated dimer of cyclo (lPhe-dHis), that of cyclo (lPhe-lHis) involves two NH⋯O interactions, forming the motif of an antiparallel β sheet. Therefore, a change in chirality of the residue prevents the formation of the β sheet pattern observed in the amyloid type aggregation. These results emphasize the peculiar role of the histidine residue in peptide structure and interaction.

Résumé: Real-time dynamics of the electronically excited open-ring isomer of 1,2-bis(2-methylbenzo[b]thiophen-3-yl)perfluorocyclopentene (BTF6) and 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)perfluorocyclopentene (PTF6) molecules was investigated using a set-up that associates a molecular beam, femtosecond lasers and velocity map imaging. The molecules were either free in the gas phase or bound to an argon cluster. DFT and TDDFT calculations were performed on BTF6. The calculated vertical excitation energies indicate an excitation by the pump laser towards a superposition of S5 and S6 states. The free molecule dynamics was found to follow a three wavepacket model. One describes the parallel conformer (P) of these molecules. It is unreactive with respect to the ring closure reaction which is responsible for the photochromic property of these molecules. It has no observable decay at the experiment time scale (up to 350 ps). The other two wavepackets describe the reactive antiparallel conformer (AP). They are formed by an early splitting of the wavepacket that was launched initially by the pump laser. They can be considered as generated by excitation of different, essentially uncoupled, deformation modes. They subsequently evolve along independent pathways. One is directed ballistically towards a conical intersection (CI) and decays through the CI to a potential energy surface where it can no longer be detected. The other fraction of the wavepacket decays also towards undetected states but in this case the driving mechanism is a non-adiabatic electronic relaxation within a potential well of the energy surfaces where it was launched. When BTF6 and PTF6 molecules are bound to an argon cluster, the same three wavepacket model applies. The vibronic relaxation timespan is enhanced by a factor 5 and a larger fraction of AP conformers follows this pathway. In contrast, the time constant associated with the ballistic movement is enhanced by only a factor of 2.

Résumé: Motivated by the major role funneling dynamics plays in light-harvesting processes, we built some laser control strategies inspired from basic mechanisms such as interference and kicks, and applied them to the case of pyrazine. We are studying
the internal conversion between the two excited states, the highest and directly reachable from the initial ground state being considered as a donor and the lowest as an acceptor. The ultimate control objective is the maximum population
deposit in the otherwise dark acceptor from a two-step process: radiative excitation of the donor, followed by a conical-intersection-mediated funneling towards the acceptor. The overall idea is to first obtain the control field param-
eters (individual pulses leading frequency and intensity, duration, and inter-pulse time delay) for tractable reduced dimensional models basically describing the conical intersection branching space. Once these parameters are optimized, they are
fixed and used in full-dimensional dynamics describing the electronic population transfer. In the case of pyrazine, the reduced model is four-dimensional, whereas the full dynamics involves 24 vibrational modes. Within experimentally achiev-
able electromagnetic field requirements, we obtain a robust control with about 60% of the ground state population deposited in the acceptor state, while about 16% remains in the donor. Moreover, we anticipate a possible transposition to the
control of even larger molecular systems, for which only a small number of normal modes are active, among all the others acting as spectators in the dynamics.

Résumé: In this paper, multidimensional dissipative quantum dynamics is studied within a system-bath approach in the Markovian regime using a model Lindblad operator. We report on the implementation of a Monte Carlo wave packet algorithm in the Heidelberg version of the Multi-Configuration Time-Dependent Hartree (MCTDH) program package, which is henceforth extended to treat stochastic dissipative dynamics. The Lindblad operator is represented as a sum of products of one-dimensional operators. The new form of the operator is not restricted to the MCTDH formalism and could be used with other multidimensional quantum dynamical methods. As a benchmark system, a two-dimensional coupled oscillators model representing the internal stretch and the surface-molecule distance in the O2/Pt(111) system coupled to a Markovian bath of electron-hole-pairs is used. The simulations reveal the interplay between coherent intramolecular coupling due to anharmonic terms in the potential and incoherent relaxation due to coupling to an environment. It is found that thermalization of the system can be approximately achieved when the intramolecular coupling is weak.

Résumé: Electronic spectra are measured for protonated carbon clusters (C2n+1H+) containing between 7 and 21 carbon atoms. Linear and cyclic C2n+1H+ isomers are separated and selected using a drift tube ion mobility stage before being mass selected and introduced into a cryogenically cooled ion trap. Spectra are measured using a two-color resonance-enhanced photodissociation strategy, monitoring C2n+1+ photofragments (H atom loss channel) as a function of excitation wavelength. The linear C7H+, C9H+, C11H+, C13H+, C15H+, and C17H+ clusters, which are predicted to have polyynic structures, possess sharp 11Σ+ ← X̃1Σ+ transitions with well-resolved vibronic progressions in C–C stretch vibrational modes. The vibronic features are reproduced by spectral simulations based on vibrational frequencies and geometries calculated with time-dependent density functional theory (ωB97X-D/cc-pVDZ level). The cyclic C15H+, C17H+, C19H+, and C21H+ clusters exhibit weak, broad transitions at a shorter wavelength compared to their linear counterparts. Wavelengths for the origin transitions of both linear and cyclic isomers shift linearly with the number of constituent carbon atoms, indicating that in both cases, the clusters possess a common structural motif.

Résumé: Halogen-containing radicals play a key role in catalytic reactions leading to stratospheric ozone destruction, thus their photochemistry is of considerable interest. Here we investigate the photodissociation dynamics of the trichloromethyl radical, CCl3 after excitation in the ultraviolet. While the primary processes directly after light absorption are followed by femtosecond-time resolved photoionisation and photoelectron spectroscopy, the reaction products are monitored by photofragment imaging using nanosecond-lasers. The dominant reaction is loss of a Cl atom, associated with a CCl2 fragment. However, the detection of Cl atoms is of limited value, because in the pyrolysis CCl2 is formed as a side product, which in turn dissociates to CCl + Cl. We therefore additionally monitored the molecular fragments CCl2 and CCl by photoionisation at 118.2 nm and disentangled the contributions from various processes. A comparison of the CCl images with control experiments on CCl2 suggest that the dissociation to CCl + Cl2 contributes to the photochemistry of CCl3.

Résumé: Grazing incidence fast atom diffraction at crystal surfaces (GIFAD or FAD) has demonstrated coherent diffraction both at effective energies close to one eV (lambda( perpendicular) approximately 14 pm for He) and at elevated surface temperatures offering high topological resolution and real time monitoring of growth processes. This is explained by a favorable Debye-Waller factor specific to the multiple collision regime of grazing incidence. This paper presents the first extensive evaluation of the temperature behavior between 177 and 1017 K on a LiF surface. Similarly to diffraction at thermal energies (TEAS), an exponential attenuation of the elastic intensity is observed but, contrarily to TEAS, the maximum coherence is not directly reduced by the attraction forces that increase the effective impact energy. It is more influenced by the surface stiffness and appears very sensitive to surface defects.

Résumé: The photoluminescence (PL) of monolayer tungsten disulfide (WS2) is locally and electrically controlled using the nonplasmonic tip and tunneling current of a scanning tunneling microscope (STM). The spatial and spectral distribution of the emitted light is determined using an optical microscope. When the STM tip is engaged, short-range PL quenching due to near-field electromagnetic effects is present, independent of the sign and value of the bias voltage applied to the tip–sample tunneling junction. In addition, a bias-voltage-dependent long-range PL quenching is measured when the sample is positively biased. We explain these observations by considering the native n-doping of monolayer WS2 and the charge carrier density gradients induced by electron tunneling in micrometer-scale areas around the tip position. The combination of wide-field PL microscopy and charge carrier injection using an STM opens up new ways to explore the interplay between excitons and charge carriers in two-dimensional semiconductors.

Résumé: Protonated cyclic dipeptides undergo collision-induced dissociation, and this reaction mechanism strongly depends on the symmetry and the nature of the residues. We review the main dissociation mechanism for a series of cyclic dipeptides, obtained through chemical dynamics simulations. The systems range from the symmetrical cyclo-(glycyl-glycyl), with two possible symmetrical protonation sites located on the peptide ring, to cyclo-(tyrosyl-prolyl), where the symmetry of protonation sites on the peptide ring is broken by the dissimilar nature of the different residues. Finally, cyclo-(phenylalanyl-histidyl) shows a completely asymmetric situation, with the proton located on one of the dipeptide side chains, which explains the peculiar fragmentation mechanism induced by shuttling the proton, whose efficiency is strongly dependent on the relative chirality of the residues.

Résumé: Iron pentacarbonyl is a textbook example of fluxionality. We trap the molecule in cryogenic matrices to study the vibrational dynamics of
CO stretching modes involved in the fluxional rearrangement. The infrared spectrum in Ar and N2 is composed of about ten narrow bands
in the spectral range of interest, indicating the population of various lattice sites and a lowering of the molecular symmetry in the trapping
sites. The vibrational dynamics is explored by means of infrared stimulated photon echoes at the femtosecond scale. Vibrational dephasing
and population relaxation times are obtained. The non-linear signals exhibit strong oscillations useful to disentangle the site composition
of the absorption spectrum. The population relaxation involves at least two characteristic times. An evolution of the photon echo signals
with the waiting time is observed. The behavior of all the signals can be reproduced within a simple model that describes the population
relaxation occurring in two steps: relaxation of v = 1 (population time T1 < 100 ps) and return to v = 0 (recovery time > 1 ns). These two steps
explain the evolution of the oscillations with the waiting time in the photon echo signals. These results discard fluxional rearrangement on
the time scale of hundreds of ps in our samples. Dephasing times are of the same order of magnitude as T1: dephasing processes due to the
matrix environment are rather inefficient. The photon echo experiments also reveal that intermolecular resonant vibrational energy transfers
between guest molecules occur at the hundreds of ps time scale in concentrated samples (guest/host > 104).

Résumé: Hypothesis
In this original work, we aim to control both the surface wetting and fluorescence properties of extremely ordered and porous conducting polymer nanotubes prepared by soft template electropolymerization and post-grafting. For reaching this aim, various substituents of different hydrophobicity and fluorescence were post-grafted and the post-grafting yields were evaluated by surface analyses. We show that the used polymer is already fluorescent before post-grafting while the post-grafting yield and as a consequence the surface hydrophobicity highly depend on the substituent.
Experiments
Here, we have chosen to chemically grafting various fluorinated and aromatic substituents using a post-grafting in order to keep the same surface topography. Flat conducting polymer surfaces with similar properties have been also prepared for determining the surface energy with the Owens-Wendt equation and estimating the post-grafting yield by X-ray Photoemission Spectroscopy (XPS) and Time of Flight Secondary Emission Spectrometry (ToF-SIMS). For example, using fluorinated chains of various length (C4F9, C6F13 and C8F17), it is demonstrated that the surface hydrophobicity and oleophobicity do not increase with the fluorinated chain length due to the different post-grafting yields and because of the presence of nanoroughness after post-grafting.
Findings
These surfaces have high apparent water contact angle up to 130.5° but also strong water adhesion, comparable to rose petal effect even if there are no nanotubes on petal surface. XPS and ToF-SIMS analyses provided a detailed characterisation of the surface chemistry with a qualitative classification of the grafted surfaces (F6 > F4 > F8). SEM analysis shows that grafting does not alter the surface morphology. Finally, fluorescence analyses show that the polymer surfaces before post-treatment are already nicely fluorescent. Although the main goal of this paper was and is to understand the role of surface chemistry in tailoring the wetting properties of these surfaces rather than provide specific application examples, we believe that the obtained results can help the development of specific nanostructured materials for potential applications in liquid transport, or in stimuli responsive antimicrobial surfaces.

Résumé: A challenging effort is under way to understand the essence of the quantum size effect of two-dimensional materials in order to achieve the ultimate goal of arbitrarily tailoring their properties in the near future. Here we present experimental and theoretical study of resonant neutralization of low-energy alkali-metal ions on clean and graphene-covered polycrystalline copper surfaces. The ion neutralization strongly depends on the number of graphene layers, and it gradually saturates for three to five layers of graphene. This result is consistent with that for the graphite surface. The neutral fraction for the clean polycrystalline copper surface is found to be significantly higher than that for the graphene-covered surface, which is not consistent with known regularities. We quantitatively explain those observations through the small energy level width of resonant electron transfer that is determined by the special electronic structure of graphene layers. This finding indicates that resonant neutralization spectroscopy has promising applications in the detection of the quantum size effects of two-dimensional materials at an atomic layer level.

Résumé: In this work, full-dimensional (9D) quantum dynamics calculations on mode-/bond-specific surface scattering of a water molecule on a copper (111) rigid surface are performed through the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method. To easily perform the ML-MCTDH calculations on such a triatomic molecule-surface system, we first choose specific Jacobi coordinates as a set of coordinates of water. Next, to efficiently perform the 9D ML-MCTDH wavepacket propagation, the potential energy surface is transferred to a canonical polyadic decomposition form with the aid of a Monte Carlo-based method. Excitation-specific dissociation probabilities of H2O on Cu(111) are computed, and mode-/bond-specific dynamics are demonstrated by comparison with a probability curve computed for a water molecule in the ground state. The dependence of the dissociation probability of the initial state of H2O is studied, and it is found that the excitation-specific dissociation probabilities can be divided into three groups. We find that the vibrationally excited states enhance the dissociation reactivity of H2O, while the rotationally excited states hardly influence it.

Résumé: The far-infrared spectrum of HC3N has been recorded at high resolution between 70 and 500 cm−1using synchrotron radiation. Four prominent features, i.e., ν7, ν6−ν7, ν4−ν6, and 2ν7 have been identified in the spectrum together with many associated hot bands. In addition, rotational transitions for the interacting v4=v7=1, (v6=2,v7=1), (v5=1,v7=2), and v7=5 vibrationally excited states have been recorded in the millimeter/submillimeter region. The newly assigned transitions, together with those reported previously, form a comprehensive data set including about 17 000 transitions, which involves almost all the vibrational states of HC3N lying below 1300 cm−1 plus some excited states with energies between 2075 and 3550 cm−1. These data have been fitted to an effective Hamiltonian which takes into account rotational and vibrational l-type resonance effects, together with a number of anharmonic interaction terms. On average, all the analysed data are reproduced within the experimental accuracy. About 90 000 rotational and ro-vibrational transition frequencies have been computed on the basis of the spectroscopic constants obtained from the global fit in order to support data interpretation and astronomical searches in the interstellar medium and planetary atmospheres. Part of these data is included in the 2020 release of the HITRAN database.

Résumé: Researchers are increasingly thinking smaller to solve some of the biggest challenges in nanomedicine: the control of drug encapsulation. Although recent years have witnessed a significant increase in the development and characterization of polymeric drug nanocarriers, several key features are still to be addressed: Where is the drug located within each nanoparticle (NP)? How much drug does each NP contain? Is the drug loading homogeneous on an individual NP basis? To answer these questions, individual NP characterization was achieved here by using atomic force microscopy-infrared spectroscopy (AFM-IR). A label-free quantification methodology was proposed to estimate with a nanoscale resolution the drug loadings of individual poly(lactic acid) (PLA) NPs loaded with an anticancer drug. First, a drug loading calibration curve was established using conventional IR microspectroscopy employing PLA/drug homogeneous films of well-known compositions. Then, single NPs were investigated by AFM-IR acquiring both IR mappings of PLA and drug as well as local IR spectra. Besides, drug location within single NPs was unravelled. The measured drug loadings were drastically different (0 to 21 wt%) from one NP to another, emphasizing the particular interest of this methodology in providing a simple quantification method for the quality control of nanomedicines.

Résumé: A combination of millimeter-wave and high-resolution infrared data is used to analyze the eight lowest-energy vibrational states of benzonitrile (C6H5CN, C2v, μa = 4.5 D), a benzene derivative recently detected in the interstellar medium. The overtone states v22 = 2 and v33 = 2, combination state v22 = 1, v33 = 1, and fundamental states v21 = 1 and v15 = 1 are studied for the first time by rotationally resolved spectroscopy. The three former states form a Coriolis- and Darling-Dennison-coupled triad of interacting states for which the coupling terms and highly precise, deperturbed energy separations have been measured. The use of sub-millimeter and far-infrared data together enabled the determination of the purely rotational and coupling parameters for the six lowest-energy vibrationally excited states of benzonitrile, along with their highly precise energies (E22 = 141.4810252 (57) cm−1, E33 = 160.5891953 (47) cm−1, E2×22 = 282.6295417 (83) cm−1, E22+33 = 302.5795909 (87) cm−1, E2×33 = 321.4923856 (77) cm−1, E21 = 372.257993 (10) cm−1). These energies, the resultant experimental anharmonicity constants (x22,22 =  − 0.1663 cm−1, x33,33 = 0.1570 cm−1, and x22,33 = 0.4909 cm−1), and semi-experimental harmonic frequencies (ω22 = 142.9 cm−1 and ω33 = 161.0 cm−1) for the ν22 and ν33 states are compared to CCSD(T)/ANO1 predicted values. The spectroscopic and coupling constants determined in this work for the vibrational ground state, the two lowest-energy fundamental states, and the corresponding first overtone and combination states successfully predict experimental frequencies down to 8 GHz. Particularly for the vibrationally excited states, the ability to predict transition frequencies so far outside the frequency region in which the constants were determined confirms that the rotational and distortion constants, as well as the coupling terms, are determined reasonably close to their true values. The ability to accurately extrapolate also demonstrates the suitability of the determined constants as the basis for extraterrestrial identification and examination of these vibrational states of benzonitrile.