CO2_2 Infrared Phonon Modes in Interstellar Ice Mixtures

CO$_2$ ice is an important reservoir of carbon and oxygen in star and planet forming regions. Together with water and CO, CO$_2$ sets the physical and chemical characteristics of interstellar icy grain mantles, including desorption and diffusion energies for other ice constituents. A detailed understanding of CO$_2$ ice spectroscopy is a prerequisite to characterize CO$_2$ interactions with other volatiles both in interstellar ices and in laboratory experiments of interstellar ice analogs. We report laboratory spectra of the CO$_2$ longitudinal optical (LO) phonon mode in pure CO$_2$ ice and in CO$_2$ ice mixtures with H$_2$O, CO, O$_2$ components. We show that the LO phonon mode position is sensitive to the mixing ratio of various ice components of astronomical interest. In the era of JWST, this characteristic could be used to constrain interstellar ice compositions and morphologies. More immediately, LO phonon mode spectroscopy provides a sensitive probe of ice mixing in the laboratory and should thus enable diffusion measurements with higher precision than has been previously possible

CO diffusion and desorption kinetics in CO2_2 ices

Diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO$_2$ ice at low temperatures (T=11--23~K) using CO$_2$ longitudinal optical (LO) phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick's second law and find the temperature dependent diffusion coefficients are well fit by an Arrhenius equation giving a diffusion barrier of 300 $\pm$ 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO$_2$ along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO$_2$ ices deposited at 11-50 K by temperature-programmed desorption (TPD) and find that the desorption barrier ranges from 1240 $\pm$ 90 K to 1410 $\pm$ 70 K depending on the CO$_2$ deposition temperature and resultant ice porosity. The measured CO-CO$_2$ desorption barriers demonstrate that CO binds equally well to CO$_2$ and H$_2$O ices when both are compact. The CO-CO$_2$ diffusion-desorption barrier ratio ranges from 0.21-0.24 dependent on the binding environment during diffusion. The diffusion-desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices

tt-Martin boundary of killed random walks in the quadrant

We compute the $t$-Martin boundary of two-dimensional small steps random walks killed at the boundary of the quarter plane. We further provide explicit expressions for the (generating functions of the) discrete $t$-harmonic functions. Our approach is uniform in $t$, and shows that there are three regimes for the Martin boundary.Comment: 18 pages, 2 figures, to appear in S\'eminaire de Probabilit\'e

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.Comment: 5 pages, 2 figures, published in ApJ

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.Comment: 21 pages 5 figure

On the dynamical behavior of the ABC model

We consider the ABC dynamics, with equal density of the three species, on the discrete ring with $N$ sites. In this case, the process is reversible with respect to a Gibbs measure with a mean field interaction that undergoes a second order phase transition. We analyze the relaxation time of the dynamics and show that at high temperature it grows at most as $N^2$ while it grows at least as $N^3$ at low temperature

The Role of Oxidation Compounds in Biofilm Growth on Polyethylene Geomembrane Barriers Used in Landfill

In a model study, polyethylene was preoxidized and incubated for a period of 7 months at 40°C in two different municipal solid waste leachates. During the postexperimental analyses, specific attention was paid to the carbonyl species and carboxylic acid depletion during the environmental exposure because it is well known that carboxylic acids are believed to be a potential substrate for the development of microorganisms. The results showed that the carbonyl as well as the carboxylic acid depletion observed follows first-order kinetics. The biofilm formation was characterized using a suite of analytical techniques, and its formation was compared with the carboxylic acid and carbonyl depletion profil

Entrepreneurial intention studies: A hybrid bibliometric method to identify new directions for theory and research

Fragmentation is the main obstacle to scientific progress on entrepreneurial intention. To address this issue, we systematise the current literature with a hybrid bibliometric method that combines co-citation and bibliographic coupling analysis for the first time in entrepreneurial intention studies to show the field's knowledge base and research fronts and to examine how divergent perspectives have challenged the core knowledge of the field. We highlight three recurring dimensions of entrepreneurial intention studies: (1) personal factors, (2) social factors and (3) investigational settings. In addition to introducing new constructs, divergent perspectives have emphasised the interplay between these components and challenged the mechanisms connecting them. Based on these findings, we extend previous classifications in the literature by providing a framework that integrates divergent perspectives with the field's knowledge base, helping establish future research avenues and improving the theorising process of entrepreneurial intention

Three osculating walkers

We consider three directed walkers on the square lattice, which move simultaneously at each tick of a clock and never cross. Their trajectories form a non-crossing configuration of walks. This configuration is said to be osculating if the walkers never share an edge, and vicious (or: non-intersecting) if they never meet. We give a closed form expression for the generating function of osculating configurations starting from prescribed points. This generating function turns out to be algebraic. We also relate the enumeration of osculating configurations with prescribed starting and ending points to the (better understood) enumeration of non-intersecting configurations. Our method is based on a step by step decomposition of osculating configurations, and on the solution of the functional equation provided by this decomposition

Long range correlations and phase transition in non-equilibrium diffusive systems

We obtain explicit expressions for the long range correlations in the ABC model and in diffusive models conditioned to produce an atypical current of particles.In both cases, the two-point correlation functions allow to detect the occurrence of a phase transition as they become singular when the system approaches the transition