Flux and fluence effects on the vacuum-UV photodesorption and photoprocessing of CO2 ices.

CO2 is a major component of the icy mantles surrounding dust grains in planet and star formation regions. Understanding its photodesorption is crucial for explaining gas phase abundances in the coldest environments of the interstellar medium irradiated by vacuum-UV (VUV) photons. Photodesorption yields determined experimentally from CO2 samples grown at low temperatures (T = 15 K) have been found to be very sensitive to experimental methods and conditions. Several mechanisms have been suggested for explaining the desorption of CO2, O2 and CO from CO2 ices. In the present study, the cross-sections characterizing the dynamics of photodesorption as a function of photon fluence (determined from released molecules in the gas phase) and of ice composition modification (determined in situ in the solid phase) are compared for the first time for different photon flux conditions (from 7.3 × 1012 photon per s cm-2 to 2.2× 1014 photon per s cm-2) using monochromatic synchrotron radiation in the VUV range (on the DESIRS beamline at SOLEIL). This approach reveals that CO and O2 desorptions are decorrelated from that of CO2. CO and O2 photodesorption yields depend on photon flux conditions and can be linked to surface chemistry. In contrast, the photodesorption yield of CO2 is independent of the photon flux conditions and can be linked to bulk ice chemical modification, consistently with indirect desorption induced by an electronic transition (DIET) process.

Mechanism of Ultraviolet-Induced CO Desorption from CO Ice: Role of Vibrational Relaxation Highlighted.

Although UV photon-induced CO ice desorption is clearly observed in many cold regions of the Universe as well as in the laboratory, the fundamental question of the mechanisms involved at the molecular scale remains debated. In particular, the exact nature of the involved energy transfers in the indirect desorption pathway highlighted in previous experiments is not explained. Using ab initio molecular dynamics simulations, we explore a new indirect desorption mechanism in which a highly vibrationally excited CO (v=40) within an aggregate of 50 CO molecules triggers the desorption of molecules at the surface. The desorption originates first from a mutual attraction between the excited molecule and the surrounding molecule(s), followed by a cascade of energy transfers, ultimately resulting in the desorption of vibrationally cold CO (∼95% in v=0). The theoretical vibrational distribution, along with the kinetic energy one, which peaks around 25 meV for CO with low rotational levels (v=0, J<7), is in excellent agreement with the results obtained from VUV laser induced desorption (157 nm) of CO (v=0, 1) probed using REMPI.

Highlights from Faraday Discussion: Astrochemistry at high resolution, Baltimore, USA, May 2023.

The Faraday Discussion 'Astrochemistry at high resolution' was held at the Space Telescope Science Institute, Baltimore, United States, and online from May 31-June 2, 2023. The meeting brought together observers, modellers, and experimentalists at different career stages and from different countries to discuss advancements in astrochemistry resulting from improved spatial resolution, spectral resolution, and sensitivity. This conference report provides highlights of the meeting and summaries of the talks presented.

Vacuum UV photodesorption of organics in the interstellar medium: an experimental study of formic acid HCOOH and methyl formate HCOOCH3-containing ices.

Being a potential process that could explain gas phase abundances of so-called complex organic molecules (COMs) in the cold interstellar medium (ISM), the UV photon-induced desorption from organics-containing molecular ices has been experimentally studied. In this work, we focused on the observation of the photodesorbed products and the measurement of the associated photodesorption yields from pure and mixed molecular ices, each containing organic molecules whose detection has been achieved in the gas phase of the cold ISM, namely formic acid HCOOH and methyl formate HCOOCH3. Each molecule, in pure ice or in ice mixed with CO or water, was irradiated at 15 K with monochromatic vacuum UV photons in the 7-14 eV range using synchrotron radiation from the SOLEIL synchrotron facility, DESIRS beamline. Photodesorption yields of the intact molecules and of the photoproducts were derived as a function of the incident photon energy. Experiments have revealed that the desorbing species match the photodissociation pattern of each isolated molecule, with little influence of the kind of ice (pure or mixed in CO or H2O-rich environment). For both species, the photodesorption of the intact organics is found to be negligible in our experimental conditions, resulting in yields typically below 10-5 ejected molecules per incident photon. The results obtained on HCOOH and HCOOCH3-containing ices are similar to what has already been found for methanol-containing ices, but contrast with the case of another complex molecule, CH3CN, photodesorption of which has been recently studied. Such experimental results may be linked to the observation of COMs in protoplanetary disks, in which CH3CN is commonly observed whereas HCOOH or methanol are detected only in some sources, HCOOCH3 not being detected at all.

Cryogenic Chemistry and Quantitative Non-Thermal Desorption from Pure Methanol Ices: High-Energy Electron versus X-Ray Induced Processes.

X-Ray irradiation of interstellar ice analogues has recently been proven to induce desorption of molecules, thus being a potential source for the still-unexplained presence of gaseous organics in the coldest regions of the interstellar medium, especially in protoplanetary disks. The proposed desorption mechanism involves the Auger decay of excited molecules following soft X-ray absorption, known as X-ray induced electron-stimulated desorption (XESD). Aiming to quantify electron induced desorption in XESD, we irradiated pure methanol (CH3 OH) ices at 23 K with 505 eV electrons, to simulate the Auger electrons originating from the O 1s core absorption. Desorption yields of neutral fragments and the effective methanol depletion cross-section were quantitatively determined by mass spectrometry. We derived desorption yields in molecules per incident electron for CO, CO2 , CH3 OH, CH4 /O, H2 O, H2 CO, C2 H6 and other less abundant but more complex organic products. We obtained desorption yields remarkably similar to XESD values.

Spectroscopic Measurements of Methane Solid-Gas Equilibrium Clapeyron Curve between 40 and 77 K.

The infrared gas-phase absorption spectrum of methane was used to determine its Clapeyron solid-gas equilibrium curve in the 40-77 K temperature range. For comparative purposes and to obtain more reliable results, two different optical experimental setups were used. At higher temperatures (53-77 K), a single pass cryogenically cooled cell was coupled to a standard low-resolution Fourier transform infrared spectrometer. The second system was a state-of-the-art vertical-external-cavity surface-emitting laser tunable source operating at around 2.3 µm, combined with a 7 m path Herriott cell, to record methane absorption features down to 40 K. From the measurements, the vapor pressure curve ln( p/Pa) = -(1191.92 ± 8.92)/( T/K) + (22.49 ± 0.16) was derived in the range 40-77 K. This corresponds to a value of 9910 ± 75 J mol-1 for the sublimation enthalpy. The relation was validated down to 40 K, increasing our knowledge of the saturation pressure by 2 orders of magnitude. Data were compared with available pressure measurements from the literature, obtained by manometric or mass spectrometry techniques, and the sublimation enthalpy was compared with a thermodynamic approach based on heat capacity measurements in the solid and gas phases.

Confinement Effects on the Nuclear Spin Isomer Conversion of H2O.

The mechanism for interconversion between the nuclear spin isomers (NSI) of H2O remains shrouded in uncertainties. The temperature dependence displayed by NSI interconversion rates for H2O isolated in an argon matrix provides evidence that confinement effects are responsible for the dramatic increase in their kinetics with respect to the gas phase, providing new pathways for o-H2O↔p-H2O conversion in endohedral compounds. This reveals intramolecular aspects of the interconversion mechanism which may improve methodologies for the separation and storage of NSI en route to applications ranging from magnetic resonance spectroscopy and imaging to interpretations of spin temperatures in the interstellar medium.

UV photodesorption of interstellar CO ice analogues: from subsurface excitation to surface desorption.

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.

Reactivity of water-electron complexes on crystalline ice surfaces.

The interactions between long-living electrons trapped in defects of crystalline D2O and electronegative molecules have been investigated using two-photon photoemission spectroscopy. When covered by a Xe adlayer, the spectroscopic signature of the trapped electrons vanishes, which provides evidence that the trapping sites are located on the surface of the crystalline ice. The reactive character of these surface-trapped electrons with molecules has been studied. In the case of CFCl3 adsorbed on top of the ice, we show that the trapped electrons induce the dissociation of the molecules, via a dissociative electron attachment process, resulting in *CFCl2 and Cl(-) formation. The latter species are responsible for the observed increase of the work function and presumably for the deactivation of the surface trapping sites with respect to subsequent light-induced population by excited electrons. This process is thought to be of high efficiency since it is observed for a very low CFCl3 coverage of only approximately 0.004 monolayer (ML). In the case of exposure of the crystalline ice to a partial pressure of gaseous O2, the deactivation of the trapping site has also been observed. The mechanism is thought to involve the formation of the O2*(-) transient anion by electron attachment, followed by its reactive interaction with the water molecules of the defect. In both cases, the mechanisms are triggered by negative ion resonances which are known from experiments using a primary electron beam to be effective for isolated molecules for ballistic electrons of approximately 0 eV. We thereby demonstrate a similarity between the processes induced by these primary, very low kinetic-energy electrons and by the long-living surface electrons on the crystalline ice surface. These results suggest that the photoexcited trapped electrons can play an important role in the heterogeneous chemical processes on condensed water surfaces and could be relevant in the polar stratosphere chemistry.

Low-serotonin levels increase delayed reward discounting in humans.

Previous animal experiments have shown that serotonin is involved in the control of impulsive choice, as characterized by high preference for small immediate rewards over larger delayed rewards. Previous human studies under serotonin manipulation, however, have been either inconclusive on the effect on impulsivity or have shown an effect in the speed of action-reward learning or the optimality of action choice. Here, we manipulated central serotonergic levels of healthy volunteers by dietary tryptophan depletion and loading. Subjects performed a "dynamic" delayed reward choice task that required a continuous update of the reward value estimates to maximize total gain. By using a computational model of delayed reward choice learning, we estimated the parameters governing the subjects' reward choices in low-, normal, and high-serotonin conditions. We found an increase of proportion in small reward choices, together with an increase in the rate of discounting of delayed rewards in the low-serotonin condition compared with the control and high-serotonin conditions. There were no significant differences between conditions in the speed of learning of the estimated delayed reward values or in the variability of reward choice. Therefore, in line with previous animal experiments, our results show that low-serotonin levels steepen delayed reward discounting in humans. The combined results of our previous and current studies suggest that serotonin may adjust the rate of delayed reward discounting via the modulation of specific loops in parallel corticobasal ganglia circuits.

Multiple model-based reinforcement learning explains dopamine neuronal activity.

A number of computational models have explained the behavior of dopamine neurons in terms of temporal difference learning. However, earlier models cannot account for recent results of conditioning experiments; specifically, the behavior of dopamine neurons in case of variation of the interval between a cue stimulus and a reward has not been satisfyingly accounted for. We address this problem by using a modular architecture, in which each module consists of a reward predictor and a value estimator. A "responsibility signal", computed from the accuracy of the predictions of the reward predictors, is used to weight the contributions and learning of the value estimators. This multiple-model architecture gives an accurate account of the behavior of dopamine neurons in two specific experiments: when the reward is delivered earlier than expected, and when the stimulus-reward interval varies uniformly over a fixed range.

Reactivity induced at 25 K by low-energy electron irradiation of condensed NH3-CH3COOD (1 : 1) mixture.

Chemical reactivity is observed following electron irradiation of a binary mixture of ammonia (NH(3)) and acetic acid (CH(3)COOD) at 25 K, without any subsequent thermal activation, as evidenced by vibrational high resolution electron energy loss spectroscopy (HREELS). Analysis of the HREEL spectra and comparison with infrared and Raman data of different molecules are compatible with glycine formation in its zwitterionic form. The onset for electron induced reaction is found to be at about approximately 13 eV. The mechanisms may involve NH radicals interaction with CH(3)COOD molecules. Then glycine formation does not imply any displacement of reactants, so that it involves only NH(3) and CH(3)COOD neighboring molecules.