arXiv subjects

H. M. Cuppen

Publications and source records attributed to H. M. Cuppen.

At least 19 recordsLinked to original sources

arXiv2026

Infrared photoprocessing of porous amorphous solid water with a free electron laser

Water ice is the most abundant ice in the interstellar medium (ISM). Previous studies on porous amorphous solid water (pASW) have shown that the infrared radiation field in the ISM modeled with infrared free electron laser (FEL) irradiation can result in changes in the ice towards a more ordered structure, characterized by a change in the OH-stretching vibration band. This paper aims to study the restructuring in more detail by varying the irradiation intensity and irradiation time for irradiations on-resonance with the OH-stretching, bending and libration modes. In addition, desorption of H2O is monitored during the irradiations. The research presented in this paper considers 42 infrared FEL irradiations on pASW samples deposited at two different rates, using the infrared FELs of the HFML-FELIX laboratory. Restructuring is studied using reflection absorption infrared (RAIR) spectroscopy, with a mass spectrometer monitoring the desorption of H2O in an ultra-high vacuum system. Desorption and restructuring occur in parallel, with the strongest effects observed for irradiation on-resonance with the OH-stretching vibration. Both processes exhibit two distinct regimes: an initial strong restructuring and desorption, characterized by an exponential decrease in the intensity of the desorption peaks within the first 5 s of irradiation, followed by a second regime of less efficient, yet continued restructuring and constant desorption in an extended area, involving energy dissipation through the hydrogen-bonding network. The trends in restructuring and desorption, depending on the absorbed energy during irradiation, are significantly different, suggesting separate processes. The astrophysical relevance of in particular the second regime of constant desorption and restructuring is discussed.

astro-ph.GA↗

arXiv2025

Molecular Mobility of Extraterrestrial Ices: Surface Diffusion in Astrochemistry and Planetary Science

Molecules are ubiquitous in space. They are necessary component in the creation of habitable planetary systems and can provide the basic building blocks of life. Solid-state processes are pivotal in the formation of molecules in space and surface diffusion in particular is a key driver of chemistry in extraterrestrial environments, such as the massive clouds in which stars and planets are formed and the icy objects within our Solar System. However, for many atoms and molecules quantitative theoretical and experimental information on diffusion, such as activation barriers, are lacking. This hinders us in unraveling chemical processes in space and determining how the chemical ingredients of planets and life are formed. In this article, an astrochemical perspective on diffusion is provided. Described are the relevant adsorbate-surface systems, the methods to model their chemical processes, and the computational and laboratory techniques to determine diffusion parameters, including the latest developments in the field. While much progress has been made, many astrochemically relevant systems remain unexplored. The complexity of ice surfaces, their temperature-dependent restructuring, and effects at low temperatures create unique challenges that demand innovative experimental approaches and theoretical frameworks. This intersection of astrochemistry and surface science offers fertile ground for physical chemists to apply their expertise. We invite the physical chemistry community to explore these systems, where precise diffusion parameters would dramatically advance our understanding of molecular evolution in space - from interstellar clouds to planetary surfaces - with implications on our understanding on the origins of life and planetary habitability.

astro-ph.SR↗

arXiv2023

Resonant infrared irradiation of CO and CH3OH interstellar ices

Solid-phase photo-processes involving icy dust grains greatly affect the chemical evolution of the interstellar medium by leading to the formation of complex organic molecules and by inducing photodesorption. So far, the focus of laboratory studies has been mainly on the impact of energetic ultraviolet (UV) photons on ices, but direct vibrational excitation by infrared (IR) photons is expected to influence the morphology and content of interstellar ices as well. However, little is still known about the mechanisms through which this excess vibrational energy is dissipated, and its implications on the structure and ice photochemistry. In this work, we present a systematic investigation of the behavior of interstellar relevant CO and CH3OH ice analogues upon resonant excitation of vibrational modes using tunable infrared radiation, leading to both the quantification of infrared-induced photodesorption and insights in the impact of vibrational energy dissipation on ice morphology. We utilize an ultrahigh vacuum setup at cryogenic temperatures to grow pure CO and CH3OH ices, as well as mixtures of the two. We expose the ices to intense, near-monochromatic mid-infrared free-electron-laser radiation to selectively excite the species. The dissipation of vibrational energy is observed to be highly dependent on the excited mode and the chemical environment of the ice. All amorphous ices undergo some degree of restructuring towards a more organized configuration upon on-resonance irradiation. Moreover, IR-induced photodesorption is observed to occur for both pure CO and CH3OH ices, with interstellar photodesorption efficiencies of the order of 10 molecules cm-2 s-1 (i.e., comparable to or higher than UV-induced counterparts). Indirect photodesorption of CO upon vibrational excitation of CH3OH in ice mixtures is also observed to occur, particularly in environments rich in methanol.

astro-ph.GA↗

arXiv2022

IRFEL Selective Irradiation of Amorphous Solid Water: from Dangling to Bulk Modes

Amorphous solid water (ASW) is one of the most widely studied solid phase systems. A better understanding of the nature of inter- and intramolecular forces in ASW is, however, still required to correctly interpret the catalytic role of ASW in the formation and preservation of molecular species in environments such as the icy surfaces of Solar System objects, on interstellar icy dust grains and potentially even in the upper layers of the Earth's atmosphere. In this work, we have systematically exposed porous ASW (pASW) to mid-infrared radiation generated by a free-electron laser at the HFML-FELIX facility in the Netherlands to study the effect of vibrational energy injection into the surface and bulk modes of pASW. During multiple sequential irradiations on the same ice spot, we observed selective effects both at the surface and in the bulk of the ice. Although the density of states in pASW should allow for a fast vibrational relaxation through the H-bonded network, part of the injected energy is converted into structural ice changes as illustrated by the observation of spectral modifications when performing Fourier transform infrared spectroscopy in reflection-absorption mode. Future studies will include the quantification of such effects by systematically investigating ice thickness, ice morphology, and ice composition.

physics.chem-ph↗

arXiv2022

Surface astrochemistry: a computational chemistry perspective

Molecules in space are synthesized via a large variety of gas-phase reactions, and reactions on dust-grain surfaces, where the surface acts as a catalyst. Especially, saturated, hydrogen-rich molecules are formed through surface chemistry. Astrochemical models have developed over the decades to understand the molecular processes in the interstellar medium, taking into account grain surface chemistry. However, essential input information for gas-grain models, such as binding energies of molecules to the surface, have been derived experimentally only for a handful of species, leaving hundreds of species with highly uncertain estimates. Moreover, some fundamental processes are not well enough constrained to implement these into the models. The proceedings gives three examples how computational chemistry techniques can help answer fundamental questions regarding grain surface chemistry.

astro-ph.GA↗

arXiv2020

A non-energetic mechanism for glycine formation in the interstellar medium

The detection of the amino acid glycine and its amine precursor methylamine on the comet 67P/Churyumov-Gerasimenko by the Rosetta mission provides strong evidence for a cosmic origin of prebiotics on Earth. How and when such complex organic molecules form along the process of star- and planet-formation remains debated. We report the first laboratory detection of glycine formed in the solid phase through atom and radical-radical addition surface reactions under cold dense interstellar cloud conditions. Our experiments, supported by astrochemical models, suggest that glycine forms without the need for energetic irradiation, such as UV photons and cosmic rays, in interstellar water-rich ices, where it remains preserved, in a much earlier star-formation stage than previously assumed. We also confirm that solid methylamine is an important side-reaction product. A prestellar formation of glycine on ice grains provides the basis for a complex and ubiquitous prebiotic chemistry in space enriching the chemical content of planet-forming material.

astro-ph.IM↗

arXiv2020

Infrared resonant vibrationally induced restructuring of amorphous solid water

Amorphous solid water (ASW) is abundantly present in the interstellar medium, where it forms a mantle on interstellar dust particles and it is the precursor for cometary ices. In space, ASW acts as substrate for interstellar surface chemistry leading to complex molecules and it is postulated to play a critical role in proton-transfer reactions. Although ASW is widely studied and is generally well characterized by different techniques, energetically-induced structural changes, such as ion, electron and photon irradiation, in these materials are less well understood. Selective pumping of specific infrared (IR) vibrational modes can aid in understanding the role of vibrations in restructuring of hydrogen bonding networks. Here we present the first experimental results on hydrogen bonding changes in ASW induced by the intense, nearly monochromatic mid-IR free-electron laser (FEL) radiation of the FELIX-2 beamline at the FELIX Laboratory at the Radboud University in Nijmegen, the Netherlands. The changes are monitored by reflection-absorption infrared spectroscopy. Upon resonant irradiation, a modification in IR absorption band profile of ASW is observed in agreement with a growing crystalline-like contribution and a decreasing amorphous contribution. This phenomenon saturates within a few minutes of FEL irradiation, modifying upwards of 94~\% of the irradiated ice. The effect is further analysed in terms of hydrogen bonding donors and acceptors and the experiments are complimented with Molecular Dynamics simulations to constrain the effect at the molecular level.

cond-mat.mtrl-sci↗

arXiv2020

Formation of COMs through CO hydrogenation on interstellar grains

Glycoaldehyde, ethylene glycol, and methyl formate are complex organic molecules that have been observed in dark molecular clouds. Because there is no efficient gas-phase route to produce these species, it is expected that a low-temperature surface route existst that does not require energetic processing. CO hydrogenation experiments at low temperatures showed that this is indeed the case. Glyoxal can form through recombination of two HCO radicals and is then further hydrogenated. Here we aim to constrain the methyl formate, glycolaldehyde, and ethylene glycol formation on the surface of interstellar dust grains through this cold and dark formation route. We also probe the dependence of the grain mantle composition on the initial gas-phase composition and the dust temperature. A full CO hydrogenation reaction network was built based on quantum chemical calculations for the rate constants and branching ratios. This network was used in combination with a microscopic kinetic Monte Carlo simulation to simulate ice chemistry, taking into account all positional information. After benchmarking the model against CO-hydrogenation experiments, simulations under molecular cloud conditions were performed. COMs are formed in all interstellar conditions we studied, even at temperatures as low as 8 K. This is because the HCO + HCO reaction can occur when HCO radicals are formed close to each other and do not require to diffuse. Relatively low abundances of methyl formate are formed. The final COM abundances depend more on the H-to-CO ratio and less on temperature. Only above 16 K, where CO build-up is less efficient, does temperature start to play a role. Molecular hydrogen is predominantly formed through abstraction reactions on the surface. Our simulations are in agreement with observed COM ratios for mantles that have been formed at low temperatures.

astro-ph.SR↗

arXiv2015

Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects

Sets of systematic laboratory experiments are presented -- combining Ultra High Vacuum cryogenic and plasma-line deposition techniques -- that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD --> OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH --> OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.

astro-ph.SR↗

arXiv2014

Diffusion-desorption ratio of adsorbed CO and CO$_2$ on water ice

Diffusion of atoms and molecules is a key process for the chemical evolution in the star forming regions of the interstellar medium. Accurate data on the mobility of many important interstellar species is however often not available and this provides a serious limitation for the reliability of models describing the physical and chemical processes in molecular clouds. Here we aim to provide the astrochemical modeling community with reliable data on the ratio between the energy barriers for diffusion and desorption for adsorbed CO and CO$_2$ on water ices. To this end, we use a fully atomistic, off-lattice kinetic Monte Carlo technique to generate dynamical trajectories of CO and CO$_2$ molecules on the surface of crystalline ice at temperatures relevant for the interstellar medium. The diffusion to desorption barrier ratios are determined to be 0.31 for CO and 0.39 for CO$_2$ . These ratios can be directly used to improve the accuracy of current gas-grain chemical models.

astro-ph.GA↗

arXiv2014

Upper limits to interstellar NH+ and para-NH2- abundances. Herschel-HIFI observations towards Sgr B2 (M) and G10.6-0.4 (W31C)

The understanding of interstellar nitrogen chemistry has improved significantly with recent results from the Herschel Space Observatory. To set even better constraints, we report here on deep searches for the NH+ ground state rotational transition J=1.5-0.5 of the ^2Pi_1/2 lower spin ladder, with fine-structure transitions at 1013 and 1019 GHz, and the para-NH2- 1_1,1-0_0,0 rotational transition at 934 GHz towards Sgr B2(M) and G10.6-0.4 using Herschel-HIFI. No clear detections of NH+ are made and the derived upper limits are <2*10^-12 and <7*10^-13 in Sgr B2(M) and G10.6-0.4, respectively. The searches are complicated by the fact that the 1013 GHz transition lies only -2.5 km/s from a CH2NH line, seen in absorption in Sgr B2(M), and that the hyperfine structure components in the 1019 GHz transition are spread over 134 km/s. Searches for the so far undetected NH2- anion turned out to be unfruitful towards G10.6-0.4, while the para-NH2- 1_1,1-0_0,0 transition was tentatively detected towards Sgr B2(M) at a velocity of 19 km/s. Assuming that the absorption occurs at the nominal source velocity of +64 km/s, the rest frequency would be 933.996 GHz, offset by 141 MHz from our estimated value. Using this feature as an upper limit, we found N(p-NH2-)<4*10^11 cm^-2. The upper limits for both species in the diffuse line-of-sight gas are less than 0.1 to 2 % of the values found for NH, NH2, and NH3 towards both sources. Chemical modelling predicts an NH+ abundance a few times lower than our present upper limits in diffuse gas and under typical Sgr B2(M) envelope conditions. The NH2- abundance is predicted to be several orders of magnitudes lower than our observed limits, hence not supporting our tentative detection. Thus, while NH2- may be very difficult to detect in interstellar space, it could, be possible to detect NH+ in regions where the ionisation rates of H2 and N are greatly enhanced.

astro-ph.GA↗

arXiv2014

Interactions of adsorbed CO$_2$ on water ice at low temperatures

We present a computational study into the adsorption properties of CO$_2$ on amorphous and crystalline water surfaces under astrophysically relevant conditions. Water and carbon dioxide are two of the most dominant species in the icy mantles of interstellar dust grains and a thorough understanding of their solid phase interactions at low temperatures is crucial for understanding the structural evolution of the ices due to thermal segregation. In this paper, a new H$_2$O-CO$_2$ interaction potential is proposed and used to model the ballistic deposition of CO$_2$ layers on water ice surfaces, and to study the individual binding sites at low coverages. Contrary to recent experimental results, we do not observe CO$_2$ island formation on any type of water substrate. Additionally, density functional theory calculations are performed to assess the importance of induced electrostatic interactions.

astro-ph.GA↗

arXiv2014

Modelling the chemical evolution of molecular clouds as a function of metallicity

The Galaxy is in continuous elemental evolution. Since new elements produced by dying stars are delivered to the interstellar medium, the formation of new enerations of stars and planetary systems is influenced by this metal enrichment. We aim to study the role of the metallicity on the gas phase chemistry of the interstellar medium. Using a system of coupled-ordinary differential equations to model the chemical reactions, we simulate the evolution of the abundance of molecules in the gas phase for different initial interstellar elemental compositions. These varying initial elemental compositions consider the change in the "elemental abundances" predicted by a self-consistent model of the elemental evolution of the Galaxy. As far as we are aware, this is the first attempt to combine elemental evolution of the Galaxy and chemical evolution of molecular clouds. The metallicity was found to have a strong effect on the overall gas phase composition. With decreasing metallicity, the number of long carbon chains was found to increase, the time-scale on which small molecular species are increases, and the main form of oxygen changed from O and CO to O2. These effects were found to be mainly due to the change in electron, H3+, and atomic oxygen abundance.

astro-ph.GA↗

arXiv2014

Dynamics of CO in Amorphous Water Ice Environments

The long-timescale behavior of adsorbed carbon monoxide on the surface of amorphous water ice is studied under dense cloud conditions by means of off-lattice, on-the-fly, kinetic Monte Carlo simula- tions. It is found that the CO mobility is strongly influenced by the morphology of the ice substrate. Nanopores on the surface provide strong binding sites which can effectively immobilize the adsorbates at low coverage. As the coverage increases, these strong binding sites are gradually occupied leav- ing a number of admolecules with the ability to diffuse over the surface. Binding energies, and the energy barrier for diffusion are extracted for various coverages. Additionally, the mobility of CO is determined from isothermal desorption experiments. Reasonable agreement on the diffusivity of CO is found with the simulations. Analysis of the 2152 cm$^{-1}$, polar CO band supports the computational findings that the pores in the water ice provide the strongest binding sites and dominate diffusion at low temperatures.

astro-ph.GA↗

arXiv2011

Molecular dynamics simulations of D2O ice photodesorption

Molecular dynamics calculations have been performed to study the ultraviolet photodissociation of D2O in an amorphous D2O ice surface at 10-90 K, in order to investigate the influence of isotope effects on the photodesorption processes. As for H2O, the main processes after UV photodissociation are trapping and desorption. There are three desorption processes: D atom, OD radical, and D2O molecule photodesorption. D2O desorption takes places either by direct desorption of a recombined D2O molecule, or when an energetic D atom produced by photodissociation kicks a surrounding D2O molecule out of the surface by transferring part of its momentum. Desorption probabilities are compared quantitatively with those for H2O obtained from previous MD simulations of UV photodissociation of amorphous water ice. The main conclusions are the same, but the average D atom photodesorption probability is smaller than that of the H atom (by about a factor of 0.9) because D has lower kinetic energy than H, whereas the average OD radical photodesorption probability is larger than that of OH (by about a factor of 2.5-2.9 depending on Tice) because OD has higher translational energy than OH for every Tice studied. The average D2O photodesorption probability is larger than that of H2O (by about a factor of 1.4-2.3 depending on Tice), and this is entirely due to a larger contribution of the D2O kick-out mechanism. This is an isotope effect: the kick-out mechanism is more efficient for D2O ice, because the D atom formed after D2O photodissociation has a larger momentum than photogenerated H atoms from H2O, and D transfers momentum more easily to D2O than H to H2O. The total yield has been compared with experiments and the total yield from previous simulations. We find better agreement when we compare experimental yields with calculated yields for D2O ice than when we compare with calculated yields for H2O ice.

physics.chem-ph↗

arXiv2010

Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalysed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.

astro-ph.GA↗

arXiv2010

Water formation at low temperatures by surface O2 hydrogenation I: characterization of ice penetration

Water is the main component of interstellar ice mantles, is abundant in the solar system and is a crucial ingredient for life. The formation of this molecule in the interstellar medium cannot be explained by gas-phase chemistry only and its surface hydrogenation formation routes at low temperatures (O, O2, O3 channels) are still unclear and most likely incomplete. In a previous paper we discussed an unexpected zeroth-order H2O production behavior in O2 ice hydrogenation experiments compared to the first-order H2CO and CH3OH production behavior found in former studies on hydrogenation of CO ice. In this paper we experimentally investigate in detail how the structure of O2 ice leads to this rare behavior in reaction order and production yield. In our experiments H atoms are added to a thick O2 ice under fully controlled conditions, while the changes are followed by means of reflection absorption infrared spectroscopy (RAIRS). The H-atom penetration mechanism is systematically studied by varying the temperature, thickness and structure of the O2 ice. We conclude that the competition between reaction and diffusion of the H atoms into the O2 ice explains the unexpected H2O and H2O2 formation behavior. In addition, we show that the proposed O2 hydrogenation scheme is incomplete, suggesting that additional surface reactions should be considered. Indeed, the detection of newly formed O3 in the ice upon H-atom exposure proves that the O2 channel is not an isolated route. Furthermore, the addition of H2 molecules is found not to have a measurable effect on the O2 reaction channel.

astro-ph.SR↗

arXiv2010

Water formation at low temperatures by surface O2 hydrogenation II: the reaction network

Water is abundantly present in the Universe. It is the main component of interstellar ice mantles and a key ingredient for life. Water in space is mainly formed through surface reactions. Three formation routes have been proposed in the past: hydrogenation of surface O, O2, and O3. In a previous paper [Ioppolo et al., Astrophys. J., 2008, 686, 1474] we discussed an unexpected non-standard zeroth-order H2O2 production behaviour in O2 hydrogenation experiments, which suggests that the proposed reaction network is not complete, and that the reaction channels are probably more interconnected than previously thought. In this paper we aim to derive the full reaction scheme for O2 surface hydrogenation and to constrain the rates of the individual reactions. This is achieved through simultaneous H-atom and O2 deposition under ultra-high vacuum conditions for astronomically relevant temperatures. Different H/O2 ratios are used to trace different stages in the hydrogenation network. The chemical changes in the forming ice are followed by means of reflection absorption infrared spectroscopy (RAIRS). New reaction paths are revealed as compared to previous experiments. Several reaction steps prove to be much more efficient (H + O2) or less efficient (H + OH and H2 + OH) than originally thought. These are the main conclusions of this work and the extended network concluded here will have profound implications for models that describe the formation of water in space.

astro-ph.SR↗