arXiv subjects

R. Dupuy

Publications and source records attributed to R. Dupuy.

7 recordsLinked to original sources

arXiv2022

\AA ngstrom depth resolution with chemical specificity at the liquid-vapor interface

The determination of depth profiles across interfaces is of primary importance in many scientific and technological areas. Photoemission spectroscopy is in principle well suited for this purpose, yet a quantitative implementation for investigations of liquid-vapor interfaces is hindered by the lack of understanding of electron-scattering processes in liquids. Previous studies have shown, however, that core-level photoelectron angular distributions (PADs) are altered by depth-dependent elastic electron scattering and can, thus, reveal information on the depth distribution of species across the interface. Here, we explore this concept further and show that the anisotropy parameter characterizing the PAD scales linearly with the average distance of atoms along the surface normal. This behavior can be accounted for in the low-collision-number regime. We also show that results for different atomic species can be compared on the same length scale. We demonstrate that atoms separated by about 1~\AA~along the surface normal can be clearly distinguished with this method, achieving excellent depth resolution.

physics.chem-ph↗

arXiv2021

X-ray induced desorption and photochemistry in CO ice

We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, are observed. In contrast, the only desorbing anions detected are O$^-$ and C$^-$. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice.

physics.chem-ph↗

arXiv2021

Mechanism of Indirect Photon-induced Desorption at the Water Ice Surface

Electronic excitations near the surface of water ice lead to the desorption of adsorbed molecules, through a so far debated mechanism. A systematic study of photon-induced indirect desorption, revealed by the spectral dependence of the desorption (7 to 13 eV), is conducted for Ar, Kr, N2, and CO adsorbed on H2O or D2O amorphous ices. The mass and isotopic dependence and the increase of intrinsic desorption efficiency with photon energy all point to a mechanism of desorption induced by collisions between adsorbates and energetic H or D atoms, produced by photodissociation of water. This constitutes a direct and unambiguous experimental demonstration of the mechanism of indirect desorption of weakly adsorbed species on water ice, and sheds new light on the possibility of this mechanism in other systems. It also has implications for the description of photon-induced desorption in astrochemical models.

physics.chem-ph↗

arXiv2021

Complex organic molecules in protoplanetary disks : X-ray photodesorption from methanol-containing ices. Part I -- Pure methanol ices

Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) 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. We aim at experimentally measuring X-ray photodesorption yields of methanol and its photo-products from pure CH$_3$OH ices, and to shed light on the mechanisms responsible for the desorption process. We irradiated methanol ices at 15 K with X-rays in the 525 - 570 eV range. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived. Under our experimental conditions, the CH$_3$OH X-ray photodesorption yield from pure methanol ice is 10$^{-2}$ molecule/photon at 564 eV. Photo-products such as CH$_4$, H$_2$CO, H$_2$O, CO$_2$ , 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. 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).

astro-ph.IM↗

arXiv2021

Complex organic molecules in protoplanetary disks: X-ray photodesorption from methanol-containing ices. Part II -- Mixed methanol-CO and methanol-H2O ices

Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) 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. We aim at experimentally measuring X-ray photodesorption yields of methanol and its photo-products from binary mixed ices: $^{13}$CO:CH$_3$OH ice and H$_2$O:CH$_3$OH ice. We irradiated these ices at 15 K with X-rays in the 525 - 570 eV range. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived. For $^{13}$CO:CH$_3$OH ice, CH$_3$OH X-ray photodesorption yield is estimated to be 10$^{-2}$ molecule/photon at 564 eV. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is detected with a yield of 10$^{-3}$ molecule/photon. When methanol is mixed with water, X-ray photodesorption of methanol and of the previous COMs is not detected. X-ray induced chemistry, dominated by low-energy secondary electrons, is found to be the main mechanism that explains these results. We also provide desorption yields that are applicable to protoplanetary disk environments for astrochemical models. The X-ray emission from YSOs should participate in the enrichment of the protoplanetary disk gas phase with COMs such as methanol in the cold and X-ray dominated regions because of X-ray photodesorption from methanol-containing ices.

astro-ph.EP↗

arXiv2020

Desorption of neutrals, cations and anions from core-excited amorphous solid water

Core-excitation of water ice releases many different molecules and ions in the gas phase. Studying these desorbed species and the underlying mechanisms can provide useful information on the effects of X-ray irradiation in ice. We report a detailed study of the X-ray induced desorption of a number of neutral, cationic and anionic species from amorphous solid water. We discuss the desorption mechanisms, and the relative contributions of Auger and secondary electrons (X-ray induced Electron Stimulated Desorption) and initial excitation (\rev{direct desorption}) as well as the role of photochemistry. Anions are shown to desorb not just through processes linked with secondary electrons but also through direct dissociation of the core-excited molecule. The desorption spectra of oxygen ions (O$^+$, OH$^+$, H$_2$O$^+$, O$^-$, OH$^-$) give a new perspective on their previously reported very low desorption yields for most types of irradiation of water, showing that they mostly originate from the dissociation of photoproducts such as H$_2$O$_2$.

physics.chem-ph↗

arXiv2017

The efficient photodesorption of nitric oxide (NO) ices A laboratory astrophysics study

The study and quantification of UV photon-induced desorption of frozen molecules furthers our understanding of the chemical evolution of cold interstellar regions. Nitric oxide (NO) is an important intermediate species in both gas-phase and solid-phase chemical networks. In this work, we present quantitative measurements of the photodesorption of a pure NO ice.We used the tunable monochromatic synchrotron light of the DESIRS beamline of the SOLEIL facility near Paris to irradiate NO ices in the 6 - 13.6 eV range and measured desorption by quadrupole mass spectrometry.We find that NO photodesorption is very efficient, its yield being around 1e-2 molecule per incident photon for UV fields relevant to the diffuse and dense interstellar medium. We discuss the extrapolation of our results to an astrophysical context and we compare photodesorption of NO to previously studied molecules.

astro-ph.GA↗