arXiv subjects

Duncan V. Mifsud

Publications and source records attributed to Duncan V. Mifsud.

15 recordsLinked to original sources

arXiv2026

Electron irradiation and temperature-programmed desorption of layered ethanolamine-water-methanol ices

Ethanolamine (EtA) is a recently detected interstellar complex organic molecule and a potential precursor to more functionalised N-bearing species. We investigate the electron-driven chemistry of layered EtA--H$_2$O--CH$_3$OH ices deposited at 20~K, combining 2~keV electron irradiation with subsequent temperature-programmed desorption (TPD) while monitoring the solid phase by mid-infrared spectroscopy. These controlled irradiation conditions represent a simplified laboratory analogue of the structural and energetic conditions within interstellar grain mantles. Volatile products released during warming were followed by quadrupole mass spectrometry, and the final residue was analysed by \textit{ex situ} electrospray ionisation mass spectrometry (ESI-MS). Irradiation produces abundant radiolysis products typical of processed methanol- and water-rich ices, including CO, CO$_2$, H$_2$CO, H$_2$O$_2$, NH$_3$, and OCN$^{-}$. Bands consistent with formic acid and polyoxymethylene-like material are also observed, indicating that carbonyl chemistry and formaldehyde-driven oligomerisation can occur alongside fragmentation in the layered system. Comparison with a choline chloride--H$_2$O reference reveals the emergence of features compatible with methylated EtA derivatives and/or choline-like species, while ESI-MS shows higher-$m/z$ mass families in the residue that are not reproduced in the substrate/background blank. However, spectral congestion and matrix effects preclude an unambiguous assignment of choline. Our results show that energetic processing of EtA-containing ices can generate a diverse inventory of O- and N-bearing products, providing laboratory constraints on radiation chemistry in cold, irradiated grain mantles under idealised conditions.

astro-ph.GA↗

arXiv2026

An interstellar energetic and non-aqueous pathway to peptide formation

The origin of the molecular building blocks of life is a central question in science. A few $α$-amino acids such as glycine, the simplest proteinogenic amino acid, have been detected in meteorites and comets, indicating an extraterrestrial origin for some prebiotic molecules. However, the formation of peptides, short chains of $α$-amino acids linked by peptide bonds, under astrophysical conditions has remained unresolved. Here we show that the building blocks of proteins can form in interstellar ice analogues exposed to ionising radiation, without the presence of liquid water. Using isotopically labelled glycine irradiated with protons at cryogenic temperatures, we detect the formation of glycylglycine, the simplest dipeptide, along with deuterated and non-deuterated water as by-products. Peptide bond formation is confirmed by infrared spectroscopy and high-resolution mass spectrometry, which also reveal the production of other complex organic species. These findings demonstrate a non-aqueous route to peptide formation under space-like conditions and suggest that such molecules could form in the cold interstellar medium and be incorporated into forming planetary systems. Our results challenge aqueous-centric models of early biochemical evolution and broaden potential settings for the origins of life.

astro-ph.SR↗

arXiv2025

Hydroxylamine in Astrophysical Ices: IR Spectra and Cosmic Ray-Induced Radiolytic Chemistry

Gas-phase hydroxylamine (NH$_2$OH) has recently been detected within dense clouds in the interstellar medium. However, it is also likely present within interstellar ices, as well as on the icy surfaces of outer Solar System bodies, where it may react to form more complex prebiotic molecules such as amino acids. In this work, we aimed to provide IR spectra of NH$_2$OH in astrophysical ice analogues that will help in the search for this molecule in various astrophysical environments. Furthermore, we aimed to provide quantitative information on the stability of NH$_2$OH upon exposure to ionizing radiation analogous to cosmic rays, as well as on the ensuing chemistry and potential formation of complex prebiotic molecules. Ices composed of NH$_2$OH, H$_2$O, and CO were prepared by vapor deposition and IR spectra were acquired between $4000-500$~cm$^{-1}$ ($2.5-20 μ$m) prior and during irradiation using 15 keV protons. In interstellar ice analogues, the most prominent IR absorption band of NH$_2$OH is that at about 1188~cm$^{-1}$, which may be a good candidate to use in searches of this species in icy space environments. Calculated effective destruction cross-sections and G-values for the NH$_2$OH-rich ices studied show that NH$_2$OH is rapidly destroyed upon exposure to ionizing radiation (more rapidly than a number of previously studied organic molecules), and that this destruction is slightly enhanced when it is mixed with other icy species. The irradiation of a NH$_2$OH:H$_2$O:CO ternary ice mixture leads to a rich chemistry that includes the formation of simple inorganic molecules such as NH$_3$, CO$_2$, OCN$^-$, and H$_2$O$_2$, as well as ammonium salts and, possibly, complex organic molecules relevant to life such as formamide, formic acid, urea, and glycine.

astro-ph.GA↗

arXiv2024

Electron Irradiation of Crystalline Nitrous Oxide Ice at Low Temperatures: Applications to Outer Solar System Planetary Science

The radiation chemistry and physics of solid N2O have been increasingly studied due to its potential presence on the surfaces of cold, outer Solar System bodies. However, to date, no study has investigated systematically the influence of temperature on this chemistry and physics. In this present study, crystalline N2O ices were irradiated using 2 keV electrons at five different temperatures in the 20-60 K range and the radiolytic dissociation of the molecular solid (as well as the radiolytic formation of seven product molecules) was quantified through the G-value. Our results indicate that temperature does indeed play a role in the radiolytic destruction of crystalline N2O, with higher temperatures being associated with higher destruction G-values. The formation G-values of NO, NO2, N2O2, N2O3, N2O4, N2O5, and O3 were also noted to vary with temperature, with each product molecule exhibiting a distinct trend. The applications of our experimental results to further understanding solid-phase radiation chemistry in the outer Solar System are discussed.

cond-mat.mtrl-sci↗

arXiv2023

Bombardment of CO ice by cosmic rays: I. Experimental insights into the microphysics of molecule destruction and sputtering

We present a dedicated experimental study of microscopic mechanisms controlling radiolysis and sputtering of astrophysical ices due to their bombardment by cosmic ray ions. Such ions are slowed down due to inelastic collisions with bound electrons, resulting in ionization and excitation of ice molecules. In experiments on CO ice irradiation, we show that the relative contribution of these two mechanisms of energy loss to molecule destruction and sputtering can be probed by selecting ion energies near the peak of the electronic stopping power. We have observed a significant asymmetry, both in the destruction cross section and the sputtering yield, for pairs of ion energies corresponding to same values of the stopping power on either side of the peak. This implies that the stopping power does not solely control these processes, as usually assumed in the literature. Our results suggest that electronic excitations represent a significantly more efficient channel for radiolysis and, possibly, also for sputtering of CO ice. We also show that the charge state of incident ions as well as the rate for CO$^+$ production in the ice have negligible effect on these processes.

astro-ph.IM↗

arXiv2023

Proton and electron irradiations of CH4:H2O mixed ices

The organic chemistry occurring in interstellar environments may lead to the production of complex molecules that are relevant to the emergence of life. Therefore, in order to understand the origins of life itself, it is necessary to probe the chemistry of carbon-bearing molecules under conditions that simulate interstellar space. Several of these regions, such as dense molecular cores, are exposed to ionizing radiation in the form of galactic cosmic rays, which may act as an important driver of molecular destruction and synthesis. In this paper, we report the results of a comparative and systematic study of the irradiation of CH4:H2O ice mixtures by 1 MeV protons and 2 keV electrons at 20 K.We demonstrate that our irradiations result in the formation of a number of new products, including both simple and complex daughter molecules such as C2H6, C3H8, C2H2, CH3OH, CO, CO2, and probably also H2CO. A comparison of the different irradiation regimes has also revealed that proton irradiation resulted in a greater abundance of radiolytic daughter molecules compared to electron irradiation, despite a lower radiation dose having been administered. These results are important in the context of the radiation astrochemistry occurring within the molecular cores of dense interstellar clouds, as well as on outer Solar System objects.

astro-ph.GA↗

arXiv2022

Energetic Electron Irradiations of Amorphous and Crystalline Sulphur-Bearing Astrochemical Ices

Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorphous phase due to the stabilising effect imparted by the presence of an extensive array of strong hydrogen bonds. These results have important consequences for the astrochemistry of interstellar ices and outer Solar System bodies, as they imply that the chemical products arising from the irradiation of amorphous ices (which may include prebiotic molecules relevant to biology) should be more abundant than those arising from similar irradiations of crystalline phases. In this present study, we have extended our work on this subject by performing comparative energetic electron irradiations of the amorphous and crystalline phases of the sulphur-bearing molecules H2S and SO2 at 20 K. We have found evidence for phase-dependent chemistry in both these species, with the radiation-induced exponential decay of amorphous H2S being more rapid than that of the crystalline phase, similar to the effect that has been previously observed for CH3OH. For SO2, two fluence regimes are apparent: a low-fluence regime in which the crystalline ice exhibits a rapid exponential decay while the amorphous ice possibly resists decay, and a high-fluence regime in which both phases undergo slow exponential-like decays.

physics.chem-ph↗

arXiv2022

Ozone Production in Electron Irradiated CO2:O2 Ices

The detection of ozone (O3) in the surface ices of Ganymede, Jupiters largest moon, and of the Saturnian moons Rhea and Dione, has motivated several studies on the route of formation of this species. Previous studies have successfully quantified trends in the production of O3 as a result of the irradiation of pure molecular ices using ultraviolet photons and charged particles (i.e., ions and electrons), such as the abundances of O3 formed after irradiation at different temperatures or using different charged particles. In this study, we extend such results by quantifying the abundance of O3 as a result of the 1 keV electron irradiation of a series of 14 stoichiometrically distinct CO2:O2 astrophysical ice analogues at 20 K. By using mid-infrared spectroscopy as our primary analytical tool, we have also been able to perform a spectral analysis of the asymmetric stretching mode of solid O3 and the variation in its observed shape and profile among the investigated ice mixtures. Our results are important in the context of better understanding the surface composition and chemistry of icy outer Solar System objects, and may thus be of use to future interplanetary space missions such as the ESA Jupiter Icy Moons Explorer and the NASA Europa Clipper missions, as well as the recently launched NASA James Webb Space Telescope.

astro-ph.EP↗

arXiv2022

Laboratory Experiments on the Radiation Astrochemistry of Water Ice Phases

Water (H2O) ice is ubiquitous component of the universe, having been detected in a variety of interstellar and Solar System environments where radiation plays an important role in its physico-chemical transformations. Although the radiation chemistry of H2O astrophysical ice analogues has been well studied, direct and systematic comparisons of different solid phases are scarce and are typically limited to just two phases. In this article, we describe the results of an in-depth study of the 2 keV electron irradiation of amorphous solid water (ASW), restrained amorphous ice (RAI) and the cubic (Ic) and hexagonal (Ih) crystalline phases at 20 K so as to further uncover any potential dependence of the radiation physics and chemistry on the solid phase of the ice. Mid-infrared spectroscopic analysis of the four investigated H2O ice phases revealed that electron irradiation of the RAI, Ic, and Ih phases resulted in their amorphization (with the latter undergoing the process more slowly) while ASW underwent compaction. The abundance of hydrogen peroxide (H2O2) produced as a result of the irradiation was also found to vary between phases, with yields being highest in irradiated ASW. This observation is the cumulative result of several factors including the increased porosity and quantity of lattice defects in ASW, as well as its less extensive hydrogen-bonding network. Our results have astrophysical implications, particularly with regards to H2O-rich icy interstellar and Solar System bodies exposed to both radiation fields and temperature gradients.

astro-ph.GA↗

arXiv2022

Comparative Electron Irradiations of Amorphous and Crystalline Astrophysical Ice Analogues

Laboratory studies of the radiation chemistry occurring in astrophysical ices have demonstrated the dependence of this chemistry on a number of experimental parameters. One experimental parameter which has received significantly less attention is that of the phase of the solid ice under investigation. In this present study, we have performed systematic 2 keV electron irradiations of the amorphous and crystalline phases of pure CH3OH and N2O astrophysical ice analogues. Radiation-induced decay of these ices and the concomitant formation of products were monitored in situ using FT-IR spectroscopy. A direct comparison between the irradiated amorphous and crystalline CH3OH ices revealed a more rapid decay of the former compared to the latter. Interestingly, a significantly lesser difference was observed when comparing the decay rates of the amorphous and crystalline N2O ices. These observations have been rationalised in terms of the strength and extent of the intermolecular forces present in each ice. The strong and extensive hydrogen-bonding network that exists in crystalline CH3OH (but not in the amorphous phase) is suggested to significantly stabilise this phase against radiation-induced decay. Conversely, although alignment of the dipole moment of N2O is anticipated to be more extensive in the crystalline structure, its weak attractive potential does not significantly stabilise the crystalline phase against radiation-induced decay, hence explaining the smaller difference in decay rates between the amorphous and crystalline phases of N2O compared to those of CH3OH. Our results are relevant to the astrochemistry of interstellar ices and icy Solar System objects, which may experience phase changes due to thermally-induced crystallisation or space radiation-induced amorphisation.

astro-ph.GA↗

arXiv2021

The Ice Chamber for Astrophysics-Astrochemistry (ICA): A New Experimental Facility for Ion Impact Studies of Astrophysical Ice Analogues

The Ice Chamber for Astrophysics-Astrochemistry (ICA) is a new laboratory end-station located at the Institute for Nuclear Research (Atomki) in Debrecen, Hungary. The ICA has been specifically designed for the study of the physico-chemical properties of astrophysical ice analogues and their chemical evolution when subjected to ionising radiation and thermal processing. The ICA is an ultra-high vacuum compatible chamber containing a series of IR-transparent substrates mounted in a copper holder connected to a closed-cycle cryostat capable of being cooled down to 20 K, itself mounted on a 360° rotation stage and a z-linear manipulator. Ices are deposited onto the substrates via background deposition of dosed gases. Ice structure and chemical composition are monitored by means of FTIR absorbance spectroscopy in transmission mode, although use of reflectance mode is possible by using metallic substrates. Pre-prepared ices may be processed in a variety of ways. A 2 MV Tandetron accelerator is capable of delivering a wide variety of high-energy ions into the ICA, which simulates ice processing by cosmic rays, the solar wind, or magnetospheric ions. The ICA is also equipped with an electron gun which may be used for electron impact radiolysis of ices. Thermal processing of both deposited and processed ices may be monitored by means of both FTIR spectroscopy and quadrupole mass spectrometry. In this paper, we provide a detailed description of the ICA set-up, as well as an overview of preliminary results obtained and future plans.

astro-ph.IM↗

arXiv2021

Electron Irradiation and Thermal Chemistry Studies of Interstellar and Planetary Ice Analogues at the ICA Astrochemistry Facility

The modelling of molecular excitation and dissociation processes relevant to astrochemistry requires the validation of theories by comparison with data generated from laboratory experimentation. The newly commissioned Ice Chamber for Astrophysics-Astrochemistry (ICA) allows for the study of astrophysical ice analogues and their evolution when subjected to energetic processing, thus simulating the processes and alterations interstellar icy grain mantles and icy outer Solar System bodies undergo. ICA is an ultra-high vacuum compatible chamber containing a series of IR-transparent substrates upon which the ice analogues may be deposited at temperatures of down to 20 K. Processing of the ices may be performed in one of three ways: (i) ion impacts with projectiles delivered by a 2 MV Tandetron-type accelerator, (ii) electron irradiation from a gun fitted directly to the chamber, and (iii) thermal processing across a temperature range of 20-300 K. The physico-chemical evolution of the ices is studied in situ using FTIR absorbance spectroscopy and quadrupole mass spectrometry. In this paper, we present an overview of the ICA facility with a focus on characterising the electron beams used for electron impact studies, as well as reporting the preliminary results obtained during electron irradiation and thermal processing of selected ices.

astro-ph.IM↗

arXiv2021

The Role of Terahertz and Far-IR Spectroscopy in Understanding the Formation and Evolution of Interstellar Prebiotic Molecules

Stellar systems are often formed through the collapse of dense molecular clouds which, in turn, return copious amounts of atomic and molecular material to the interstellar medium. An in-depth understanding of chemical evolution during this cyclic interaction between the stars and the interstellar medium is at the heart of astrochemistry. Systematic chemical composition changes as interstellar clouds evolve from the diffuse stage to dense, quiescent molecular clouds to star-forming regions and proto-planetary disks further enrich the molecular diversity leading to the evolution of ever more complex molecules. In particular, the icy mantles formed on interstellar dust grains and their irradiation are thought to be the origin of many of the observed molecules, including those that are deemed to be prebiotic; that is those molecules necessary for the origin of life. This review will discuss both observational (e.g., ALMA, SOFIA, Herschel) and laboratory investigations using millimeter, submillimeter, and terahertz and far-IR (THz/F-IR) spectroscopies and the role that they play in contributing to our understanding of the formation of prebiotic molecules. Mid-IR spectroscopy has typically been the primary tool used in laboratory studies. However, THz/F-IR spectroscopy offers an additional and complementary approach in that it provides the ability to investigate intermolecular interactions compared to the intramolecular modes available in the mid-IR. THz/F-IR spectroscopy is still somewhat under-utilized, but with the additional capability it brings, its popularity is likely to significantly increase in the near future. This review will discuss the strengths and limitations of such methods, and will also provide some suggestions on future research areas that should be pursued in the coming decade exploiting both space-borne and laboratory facilities.

astro-ph.GA↗

arXiv2021

Systems Astrochemistry: A New Doctrine for Experimental Studies

Laboratory experiments play a key role in deciphering the chemistry of the interstellar medium (ISM) and the role that product complex organic molecules (COMs) may play in the origins of life. However, to date, most studies in experimental astrochemistry have made use of reductionist approaches to experimental design in which chemical responses to variations in a single parameter are investigated while all other parameters are held constant. Although such work does afford insight into the chemistry of the ISM, it is likely that several important points, such as the relative importance of an experimental parameter in determining the chemical outcome of a reaction and the interaction between parameters, remain ambiguous. In light of this, we propose adopting a new systems astrochemistry framework for experimental studies which draws on current work performed in the field of prebiotic chemistry, and present the basic tenants of such an approach in this article. This systems approach would focus on the emergent properties of the chemical system by performing the simultaneous variation of multiple experimental parameters and would allow for the effect of each parameter, as well as their interactions, to be quantified. We anticipate that the application of systems science to laboratory astrochemistry, coupled with developments in hyphenated analytical techniques and data analytics, will uncover significant new data hitherto unknown, and will aid in better linking laboratory experiments to observations and modelling work.

astro-ph.EP↗

arXiv2021

Sulfur Ice Astrochemistry: A Review of Laboratory Studies

Sulfur is the tenth most abundant element in the universe and is known to play a significant role in biological systems. Accordingly, in recent years there has been increased interest in the role of sulfur in astrochemical reactions and planetary geology and geochemistry. Among the many avenues of research currently being explored is the laboratory processing of astrophysical ice analogues. Such research involves the synthesis of an ice of specific morphology and chemical composition at temperatures and pressures relevant to a selected astrophysical setting (such as the interstellar medium or the surfaces of icy moons). Subsequent processing of the ice under conditions that simulate the selected astrophysical setting commonly involves radiolysis, photolysis, thermal processing, neutral-neutral fragment chemistry, or any combination of these, and has been the subject of several studies. The in-situ changes in ice morphology and chemistry occurring during such processing has been monitored via spectroscopic or spectrometric techniques. In this paper, we have reviewed the results of laboratory investigations concerned with sulfur chemistry in several astrophysical ice analogues. Specifically, we review (i) the spectroscopy of sulfur-containing astrochemical molecules in the condensed phase, (ii) atom and radical addition reactions, (iii) the thermal processing of sulfur-bearing ices, (iv) photochemical experiments, (v) the non-reactive charged particle radiolysis of sulfur-bearing ices, and (vi) sulfur ion bombardment of and implantation in ice analogues. Potential future studies in the field of solid phase sulfur astrochemistry are also discussed in the context of forthcoming space missions, such as the NASA James Webb Space Telescope and the ESA Jupiter Icy Moons Explorer mission.

astro-ph.EP↗