arXiv subjects

Mathieu Bertin

Publications and source records attributed to Mathieu Bertin.

15 recordsLinked to original sources

arXiv2026

Temperature-programmed desorption of SO2 from water ice surfaces: Adsorption energy distributions

Context. Sulphur-bearing species play a key role in the chemical evolution of the interstellar medium and icy Solar System bodies such as the Jovian moons, yet the sulphur budget remains poorly constrained. Sulphur dioxide is considered one of the main sulphur reservoirs in icy environments, making its interaction with water ice surfaces highly relevant for astrochemical models. Aims. This work aims to extract adsorption energy distributions of SO2 on water ice substrates as a relevant model for astrophysical environments to better constrain its thermal behaviour and solid-gas exchange for astrochemical simulations. Methods. We performed a systematic experimental study of temperature-programmed desorption of SO2 deposited on three types of surfaces -- polycrystalline gold, compact amorphous solid water (c-ASW), and crystalline water under ultra-high vacuum conditions -- to then extract, using a Polanyi-Wigner model, the adsorption energy distributions of SO2 on each surface. Results. We performed the extraction of the adsorption energy distribution of SO2 deposited on water ice substrates. These exhibit a bimodal structure: a first physisorbed layer and a second, more strongly bound population. Only minor differences are observed between c-ASW and crystalline water ice in the behaviour of the distributions. We also provide mean values, most probable values, and width of the distribution. On average, the binding energy of SO2 on water ice surface is 439 +- 41 meV.

astro-ph.GA↗

arXiv2025

Deep Potential-Driven Molecular Dynamics of CO Ice Analogues: Investigating Desorption Following Vibrational Excitation

We present a new deep learning-based machine learning potential (MLP) for molecular dynamics simulations of solid carbon monoxide (CO), capable of accurately describing CO vibrations both in the fundamental state and in highly excited vibrational states, up to approximately v = 40. The MLP is based on the combination of high-dimensional neural network atomic potentials using the DeePMD-kit package, trained on prior ab initio molecular dynamics (AIMD) data, with selective treatment of the excited molecule allowing us to capture complex energy redistribution dynamics in condensed-phase environments. In particular, the MLP is capable of accurately describing the desorption process of a single CO molecule within an aggregate of 50 CO molecules, in excellent agreement with both previous theoretical predictions and experimental measurements. The MLP provides a much finer description of the translational and rotational energy distributions, capturing their character with high fidelity and allowing a more detailed comparison with experimental results. Furthermore, the analysis of the rotational energy, resolved over specific translational energies, revealed new insights into the coupling between translational and rotational degrees of freedom during the photodesorption process. This novel approach opens new perspectives for extensive statistical studies on desorption energies and detailed investigations of surface molecule excitations and the exploration of larger-scale models incorporating periodic boundary conditions to simulate more realistic CO aggregates.

physics.chem-ph↗

arXiv2024

Flux and fluence effects on the Vacuum-UV photodesorption and photoprocessing of CO$_2$ ices

CO$_2$ 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 CO$_2$ 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 CO$_2$, O$_2$ and CO from CO$_2$ 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$\times 10^{12}$~photon/s/cm$^2$ to 2.2$\times 10^{14}$~photon/s/cm$^2$) using monochromatic synchrotron radiation in the VUV range (on the DESIRS beamline at SOLEIL). This approach reveals that CO and O$_2$ desorption are decorrelated from that of CO$_2$. CO and O$_2$ photodesorption yields depend on photon flux conditions and can be linked to surface chemistry. By contrast, the phodesorption yield of CO$_2$ is independent of the photon flux conditions and can be linked to bulk ice chemical modification, consistently with an indirect desorption induced by electronic transition (DIET) process.

astro-ph.GA↗

arXiv2021

Photodesorption of acetonitrile CH3CN in UV-irradiated regions of the Interstellar Medium: an experimental evidence

Pure acetonitrile (CH3CN) and mixed CO:CH3CN and H2O:CH3CN ices have been irradiated at 15K with Vacuum UltraViolet (VUV) photons in the 7-13.6 eV range using synchrotron radiation. VUV photodesorption yields of CH3CN and of photo-products have been derived as a function of the incident photon energy. The coadsorption of CH3CN with CO and H2O molecules, which are expected to be among the main constituents of interstellar ices, is found to have no significant influence on the VUV photodesorption spectra of CH3CN, CHCN, HCN, CN and CH3. Contrary to what has generally been evidenced for most of the condensed molecules, these findings point toward a desorption process for which the CH3CN molecule that absorbs the VUV photon is the one desorbing. It can be ejected in the gas phase as intact CH3CN or in the form of its photo-dissociation fragments. Astrophysical VUV photodesorption yields, applicable to different locations, are derived and can be incorporated into astrochemical modeling. They vary from 0.67(+/-0.33).10^{-5} to 2.0(+/-1.0).10^{-5} molecule/photon for CH3CN depending on the region considered, which is high compared to other organic molecules such as methanol. These results could explain the multiple detections of gas phase CH3CN in different regions of the interstellar medium and are well-correlated to astrophysical observations of the Horsehead nebula and of protoplanetary disks (such as TW Hya and HD 163296).

astro-ph.GA↗

arXiv2021

Vacuum-UV photodesorption from compact Amorphous Solid Water : photon energy, isotopic and temperature effects

Vacuum-UV (VUV) photodesorption from water-rich ice mantles coating interstellar grains is known to play an important role in the gas-to-ice ratio in star- and planet-forming regions. Quantitative photodesorption yields from water ice are crucial for astrochemical models. We aim to provide the first quantitative photon-energy dependent photodesorption yields from water ice in the VUV. This information is important to understand the photodesorption mechanisms and to account for the variation of the yields under interstellar irradiation conditions. Experiments have been performed on the DESIRS beamline at the SOLEIL synchrotron, delivering tunable VUV light, using the SPICES (Surface Processes and ICES) set-up. Compact amorphous solid water ice (H$_2$O and D$_2$O) has been irradiated from 7 to 13.5 eV. Quantitative yields have been obtained by detection in the gas phase with mass-spectrometry for sample temperatures ranging from 15 K to 100 K. Photodesorption spectra of H$_2$O (D$_2$O), OH (OD), H$_2$ (D$_2$) and O$_2$ peak around 9-10 eV and decrease at higher energies. Average photodesorption yields of intact water at 15 K are 5 $\times$ 10$^{-4}$ molecule/photon for H$_2$O and 5 $\times$ 10$^{-5}$ molecule/photon for D$_2$O over the 7-13.5 eV range. The strong isotopic effect can be explained by a differential chemical recombination between OH (OD) and H (D) photofragments originating from lower kinetic energy available for the OH photofragments upon direct water photodissociation and/or possibly by an electronic relaxation process. It is expected to contribute to water fractionation during the building-up of the ice grain mantles in molecular clouds and to favor OH-poor chemical environment in comet-formation regions of protoplanetary disks. The yields of all the detected species except OH (OD) are enhanced above (70 $\pm$10) K, suggesting an ice restructuration at this temperature.

physics.chem-ph↗

arXiv2019

Vacuum ultraviolet photodesorption and photofragmentation of formaldehyde-containing ices

Non-thermal desorption from icy grains containing H$_2$CO has been invoked to explain the observed H$_2$CO gas phase abundances in ProtoPlanetary Disks (PPDs) and Photon Dominated Regions (PDRs). Photodesorption is thought to play a key role, however no absolute measurement of the photodesorption from H$_2$CO ices were performed up to now, so that a default value is used in the current astrophysical models. As photodesorption yields differ from one molecule to the other, it is crucial to experimentally investigate photodesorption from H$_2$CO ices. We measured absolute wavelength-resolved photodesorption yields from pure H$_2$CO ices, H$_2$CO on top of a CO ice (H$_2$CO/CO), and H$_2$CO mixed with CO ice (H$_2$CO:CO) irradiated in the Vacuum UltraViolet (VUV) range (7-13.6~eV). Photodesorption from a pure H$_2$CO ice releases H$_2$CO in the gas phase, but also fragments, such as CO and H$_2$. Energy-resolved photodesorption spectra, coupled with InfraRed (IR) and Temperature Programmed Desorption (TPD) diagnostics, showed the important role played by photodissociation and allowed to discuss photodesorption mechanisms. For the release of H$_2$CO in the gas phase, they include Desorption Induced by Electronic Transitions (DIET), indirect DIET through CO-induced desorption of H$_2$CO and photochemical desorption. We found that H$_2$CO photodesorbs with an average efficiency of $\sim 4-10 \times 10^{-4}$ molecule/photon, in various astrophysical environments. H$_2$CO and CO photodesorption yields and photodesorption mechanisms, involving photofragmentation of H$_2$CO, can be implemented in astrochemical codes. The effects of photodesorption on gas/solid abundances of H$_2$CO and all linked species from CO to Complex Organic Molecules (COMs), and on the H$_2$CO snowline location, are now on the verge of being unravelled.

astro-ph.GA↗

arXiv2018

Synchrotron radiation interaction with cryosorbed layers for astrochemical investigations

Photon-stimulated desorption (PSD) is a process of interest for the two seemingly unrelated topics of accelerator vacuum dynamics and astrochemistry. Here we present an approach to studying PSD of interstellar ice analogs, i.e. condensed films of molecules of astrophysical interest at cryogenic temperatures, using synchrotron radiation. We present results obtained in the VUV range on various pure and layered ices, focusing on elucidating the desorption mechanisms, and results in the X-ray range for H$_2$O.

astro-ph.GA↗

arXiv2018

X-ray photodesorption from water ice in protoplanetary disks and X-ray dominated regions

Water is the main constituent of interstellar ices, and it plays a key role in the evolution of many regions of the interstellar medium, from molecular clouds to planet-forming disks. In cold regions of the ISM, water is expected to be completely frozen out onto the dust grains. Nonetheless, observations indicate the presence of cold water vapor, implying that non-thermal desorption mechanisms are at play. Photodesorption by UV photons has been proposed to explain these observations, with the support of extensive experimental and theoretical work on ice analogues. In contrast, photodesorption by X-rays, another viable mechanism, has been little studied. The potential of this process to desorb key molecules, such as water, intact rather than fragmented or ionised, remains unexplored. We experimentally investigated X-ray photodesorption from water ice, monitoring all desorbing species. We find that desorption of neutral water is efficient, while ion desorption is minor. We derive for the first time yields that can be implemented in astrochemical models. These results open up the possibility of taking into account the X-ray photodesorption process in the modelling of protoplanetary disks or X-ray dominated regions.

astro-ph.GA↗

arXiv2017

Nitrile versus isonitrile adsorption at interstellar grain surfaces II. Carbonaceous aromatic surfaces

Almost 20 % of the ~ 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH$_3$CN and CH$_3$NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption (TPD) in an ultra-high vacuum (UHV) between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory (DFT) to represent the organised solid support. The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50\% as compared to adsorption on perfect graphene planes. The most stable isomer (CH$_3$CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH$_3$NC), however.

astro-ph.GA↗

arXiv2017

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules is monitored and quantified. Methods. Tunable monochromatic VUV light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7 - 13.6 eV (177 - 91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry and absolute photodesorption yields of intact CH4 are deduced. Results. CH4 photodesorbs for photon energies higher than ~9.1 eV (~136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions. The photodesorption of CH4 from the pure ice in various interstellar environments is around 2.0 x 10^-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles.

astro-ph.GA↗

arXiv2016

Nitrile versus isonitrile adsorption at interstellar grains surfaces: I - Hydroxylated surfaces

Almost 20% of the ~ 200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Among these 37 molecules, 30 are nitrile R-CN compounds, the remaining seven belonging to the isonitrile R-NC family. How these species behave in presence of the grain surfaces is still an open question. In this contribution we investigate whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of different nature and morphologies. The question was addressed by means of a concerted experimental and theoretical study of the adsorption energies of CH3CN and CH3NC on the surface water ice and silica. The experimental determination of the molecule - surface interaction energies was carried out using temperature programmed desorption (TPD) under an ultra-high vacuum (UHV) between 70 and 160 K. Theoretically, the question was addressed using first principle periodic density functional theory (DFT) to represent the organized solid support. The most stable isomer (CH3CN) interacts more efficiently with the solid support than the higher energy isomer (CH3NC) for water ice and silica. Comparing with the HCN and HNC pair of isomers, the simulations show an opposite behaviour, in which isonitrile HNC are more strongly adsorbed than nitrile HCN provided that hydrogen bonds are compatible with the nature of the model surface. The present study confirms that the strength of the molecule surface interaction between isomers is not related to their intrinsic stability but instead to their respective ability to generate different types of hydrogen bonds.

astro-ph.GA↗

arXiv2016

UV photodesorption of methanol in pure and CO-rich ices: desorption rates of the intact molecule and of the photofragments

Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH$_3$OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH$_3$, OH, H$_2$CO and CH$_3$O/CH$_2$OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH$_3$O, therefore opening new gas phase chemical routes for the formation of complex molecules.

astro-ph.GA↗

arXiv2013

Indirect ultraviolet photodesorption from CO:N2 binary ices - an efficient grain-gas process

UV ice photodesorption is an important non-thermal desorption pathway in many interstellar environments that has been invoked to explain observations of cold molecules in disks, clouds and cloud cores. Systematic laboratory studies of the photodesorption rates, between 7 and 14 eV, from CO:N2 binary ices, have been performed at the DESIRS vacuum UV beamline of the synchrotron facility SOLEIL. The photodesorption spectral analysis demonstrates that the photodesorption process is indirect, i.e. the desorption is induced by a photon absorption in sub-surface molecular layers, while only surface molecules are actually desorbing. The photodesorption spectra of CO and N2 in binary ices therefore depend on the absorption spectra of the dominant species in the subsurface ice layer, which implies that the photodesorption efficiency and energy dependence are dramatically different for mixed and layered ices compared to pure ices. In particular, a thin (1-2 ML) N2 ice layer on top of CO will effectively quench CO photodesorption, while enhancing N2 photodesorption by a factors of a few (compared to the pure ices) when the ice is exposed to a typical dark cloud UV field, which may help to explain the different distributions of CO and N2H+ in molecular cloud cores. This indirect photodesorption mechanism may also explain observations of small amounts of complex organics in cold interstellar environments.

astro-ph.GA↗

arXiv2013

Wavelength-dependent UV photodesorption of pure N2 and O2 ices

Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. N2 photodesorption mainly occurs through excitation of the b^1Pi_u state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7 - 13.6 eV range occurs through dissociation and presents no vibrational structure. Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10E-3 and 10E-2 photodesorbed molecules per incoming photon.

astro-ph.GA↗

arXiv2011

CO ice photodesorption: A wavelength-dependent study

UV-induced photodesorption of ice is a non-thermal evaporation process that can explain the presence of cold molecular gas in a range of interstellar regions. Information on the average UV photodesorption yield of astrophysically important ices exists for broadband UV lamp experiments. UV fields around low-mass pre-main sequence stars, around shocks and in many other astrophysical environments are however often dominated by discrete atomic and molecular emission lines. It is therefore crucial to consider the wavelength dependence of photodesorption yields and mechanisms. In this work, for the first time, the wavelength-dependent photodesorption of pure CO ice is explored between 90 and 170 nm. The experiments are performed under ultra high vacuum conditions using tunable synchrotron radiation. Ice photodesorption is simultaneously probed by infrared absorption spectroscopy in reflection mode of the ice and by quadrupole mass spectrometry of the gas phase. The experimental results for CO reveal a strong wavelength dependence directly linked to the vibronic transition strengths of CO ice, implying that photodesorption is induced by electronic transition (DIET). The observed dependence on the ice absorption spectra implies relatively low photodesorption yields at 121.6 nm (Ly-alpha), where CO barely absorbs, compared to the high yields found at wavelengths coinciding with transitions into the first electronic state of CO (singulet Pi at 150 nm); the CO photodesorption rates depend strongly on the UV profiles encountered in different star formation environments.

astro-ph.GA↗