Alexander Rosu-Finsen

Photodesorption and physical properties of CO ice as a function of temperature

Context. Ice photodesorption has been the topic of recent studies that aim to interpret the abundances of gas-phase molecules, in particular CO, toward cold interstellar regions. But little is known about the effect of the ice’s physical properties on the photodesorption rate. The linear decrease observed in the photodesorption rate, as a function of increasing CO ice deposition temperature, was provisionally attributed to a more compact CO ice structure. Aims. The goal of this work is to monitor the physical properties of solid CO as a function of ice deposition temperature. Then, we evaluate the possible link between the structure of ice and the ice’s photodesorption rate. Methods. Infrared spectroscopy is an efficient tool to monitor the structural evolution of pure ices during warm-up or irradiation. The infrared absorption bands of molecular ice components observed toward various space environments allow for the detection of H 2 O, CO, CO 2 , CH 3 OH, NH 3 , etc. Typically, a pure ice that is composed of one of these species displays significant changes in their mid-infrared band profiles as a result of warm-up. But, at most, only very subtle changes appear in the narrow CO ice infrared absorption band as the result of warm-up. We, therefore, also used vacuum-ultraviolet spectroscopy of CO ice to monitor the effect of temperature in the physical properties of the ice. Finally, temperature-programmed desorption and photo-desorption experiments for different CO ice deposition temperatures were performed. Results. Mid-infrared and vacuum-ultraviolet spectroscopy showed that warm-up of CO ice that is deposited at 8 K did not lead to structural changes. Only CO ice samples deposited at temperatures above 20 K displayed different spectroscopic properties compared to lower deposition temperatures. The observed gradual and linear drop in the photodesorption rate of CO ice, as a function of increasing ice deposition temperature in the 7 to 20 K range, is, therefore, not due to a gradual re-structuring toward a more compact and crystalline ice, which is only triggered above 20 K and increases for higher deposition temperatures. Conclusions. We suggest that this decrease of the photodesorption rate is related to the disorder of CO dipole molecules within the amorphous or glassy state, which influences the necessary transfer of photon energy from the first excited molecule to the desorbing molecule on the ice surface. The photodesorption yield of CO deposited at 20 K is about four times lower than at 7 K. Dust models should adopt CO photodesorption yields that are compatible with the thermal history of the cloud.

Laboratory surface astrochemistry experiments

Although several research groups have studied the formation of H2 on interstellar dust grains using surface science techniques, few have explored the formation of more complex molecules. A small number of these reactions produce molecules that remain on the surface of interstellar dust grains and, over time, lead to the formation of icy mantles. The most abundant of these species within the ice is H2O and is of particular interest as the observed molecular abundance cannot be accounted for using gas-phase chemistry alone. This article provides a brief introduction to the astronomical implications and motivations behind this research and the requirement for a new dual atomic beam ultrahigh vacuum (UHV) system. Further details of the apparatus design, characterisation, and calibration of the system are provided along with preliminary data from atomic O and O2 beam dosing on bare silica substrate and subsequent temperature programmed desorption measurements. The results obtained in this ongoing research may enable more chemically accurate surface formation mechanisms to be deduced for this and other species before simulating the kinetic data under interstellar conditions.

Laboratory investigations of irradiated acetonitrile-containing ices on an interstellar dust analog

Reflection-absorption infrared spectroscopy is used to study the impact of low-energy electron irradiation of acetonitrile-containing ices, under conditions close to those in the dense star-forming regions in the interstellar medium. Both the incident electron energy and the surface coverage were varied. The experiments reveal that solid acetonitrile is desorbed from its ultrathin solid films with a cross section of the order of 10−17 cm2. Evidence is presented for a significantly larger desorption cross section for acetonitrile molecules at the water–ice interface, similar to that previously observed for the benzene–water system.

Spontaneous electric fields in solid carbon monoxide.

Reflection-absorption infrared spectroscopy (RAIRS) is shown to provide a means of observing the spontelectric phase of matter, the defining characteristic of which is the occurrence of a spontaneous and powerful static electric field within a film of material. The presence of such a field is demonstrated here through the study of longitudinal-transverse optical splitting in RAIR spectra in films of carbon monoxide, based upon the deposition temperature dependence of this splitting. Analysis of spectral data, in terms of the vibrational Stark effect, allows the measurement of the polarization of spontelectric films, showing for example that solid carbon monoxide at 20 K may maintain a spontelectric field of 3.78 × 10(7) V m(-1), representing a polarization of 3.34 × 10(-4) cm(-2). We comment on the astrophysical implications of polarized carbon monoxide ices, on the surface of cosmic grains in star-forming regions.

ENABLING STAR FORMATION VIA SPONTANEOUS MOLECULAR DIPOLE ORIENTATION IN ICY SOLIDS

It is shown here how new experimental data, for the electrical properties of solid CO, can be used to fill important gaps in our understanding of the evolution of prestellar cores. Dust grains with a mantle of CO lead to a reduction in the degree of ionization in these cores by a factor of between 5 and 6. The lifetimes for expulsion of magnetic fields from cores, a process generally necessary for gravitational collapse, are reduced from current estimates of several megayears, by a similar factor. This removes a major inconsistency, since lifetimes now tally with typical ages of prestellar cores of a few hundred thousand to 106 yr, derived from observations. With the reduced timescales, cores also escape disruption by Galactic supernova remnants. Our results provide a natural mechanism for the generation of so-called magnetically supercritical cores, in which the magnetic field alone cannot prevent gravitational collapse. In addition, we find a minimum value for the density of prestellar cores of ≥(1.1 ± 0.1) × 104 H2 cm−3, in agreement with observations.

Wannier-Mott Excitons in Nanoscale Molecular Ices

The absorption of light to create Wannier-Mott excitons is a fundamental feature dictating the optical and photovoltaic properties of low band gap, high permittivity semiconductors. Such excitons, with an electron-hole separation an order of magnitude greater than lattice dimensions, are largely limited to these semiconductors but here we find evidence of Wannier-Mott exciton formation in solid carbon monoxide (CO) with a band gap of >8  eV and a low electrical permittivity. This is established through the observation that a change of a few degrees K in deposition temperature can shift the electronic absorption spectra of solid CO by several hundred wave numbers, coupled with the recent discovery that deposition of CO leads to the spontaneous formation of electric fields within the film. These so-called spontelectric fields, here approaching 4×10^{7}  V m^{-1}, are strongly temperature dependent. We find that a simple electrostatic model reproduces the observed temperature dependent spectral shifts based on the Stark effect on a hole and electron residing several nm apart, identifying the presence of Wannier-Mott excitons. The spontelectric effect in CO simultaneously explains the long-standing enigma of the sensitivity of vacuum ultraviolet spectra to the deposition temperature.

Peeling the astronomical onion

Water ice is the most abundant solid in the Universe. Understanding the formation, structure and multiplicity of physicochemical roles for water ice in the cold, dense interstellar environments in which it is predominantly observed is a crucial quest for astrochemistry as these are regions active in star and planet formation. Intuitively, we would expect the mobility of water molecules deposited or synthesised on dust grain surfaces at temperatures below 50 K to be very limited. This work delves into the thermally-activated mobility of H2O molecules on model interstellar grain surfaces. The energy required to initiate this process is studied by reflection-absorption infrared spectroscopy of small quantities of water on amorphous silica and highly oriented pyrolytic graphite surfaces as the surface is annealed. Strongly non-Arrhenius behaviour is observed with an activation energy of 2 kJ mol-1 on the silica surface below 25 K and 0 kJ mol-1 on both surfaces between 25 and 100 K. The astrophysical implication of these results is that on timescales shorter than that estimated for the formation of a complete monolayer of water ice on a grain, aggregation of water ice will result in a non-uniform coating of water, hence leaving bare grain surface exposed. Other molecules can thus be formed or adsorbed on this bare surface.