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We studied the isotopic composition of ozone formed at low (3-10 K) temperature via O + O2 solid state reactions using a partially dissociated 16O/16O2 : 18O/18O2 = 1 : 1 mixture. The ozone ice has an isotopic abundance that differs from the statistical one and from gas phase studies. Ozone formation is influenced by the competition of the production of O2 (O + O or O + O3) vs. O3 (O + O2) and by the energy released in the O + O reaction. The exothermicity of the O + O reaction helps to overcome the barrier of the O + O2 reaction. Heating the ozone ice past 50 K brings about a transformation from amorphous to crystalline ice. The formation of ozone on water ice yields a blue shift of IR bands, and the yield of formed O3 increases up to the sample temperature of 100 K. When 18O/18O2 is deposited on H216O ice, formation of 18O18O16O is detected. We propose that the exothermicity of the reaction 18O + 18O drives water dissociation (16O + H2) followed by ozone formation (16O + 18O2 → 16O18O18O).

We study the adsorption and desorption of three isotopologues of molecular hydrogen mixed on 10 ML of porous amorphous water ice (ASW) deposited at 10 K. Thermally programmed desorption (TPD) of H2, D2 and HD adsorbed at 10 K have been performed with different mixings. Various coverages of H2, HD and D2 have been explored and a model taking into account all species adsorbed on the surface is presented in detail. The model we propose allows to extract the parameters required to fully reproduce the desorption of H2, HD and D2 for various coverages and mixtures in the sub-monolayer regime. The model is based on a statistical description of the process in a grand-canonical ensemble where adsorbed molecules are described following a Fermi-Dirac distribution.

We observe photoabsorption of the W(1) ← X(0) band in five carbon monoxide isotopologues with a vacuum-ultraviolet Fourier-transform spectrometer and a synchrotron radiation source. We deduce transition energies, integrated cross sections, and natural linewidths of the observed rotational transitions and find a perturbation affecting these. Following a deperturbation analysis of all five isotopologues, the perturbing state is assigned to the v = 0 level of a previously unobserved (1)Π state predicted by ab initio calculations to occur with the correct symmetry and equilibrium internuclear distance. We label this new state E″ (1)Π. Both of the interacting levels W(1) and E″(0) are predissociated, leading to dramatic interference effects in their corresponding linewidths.

We present high-resolution absorption spectral measurements of the A(1)Π-X(1)Σ(+) band system of (13)C(16)O. These were recorded with the VUV Fourier transform spectrometer (VUV-FTS) installed on the DESIRS beamline at the SOLEIL synchrotron. This work includes revised term values that extend to higher J' values than previous measurements for most v' levels and lower J' values for v' = 0. We confirm previously observed perturbations of the rotational levels in greater detail and present evidence for new perturbations. The accuracy in the wavelength determination and term values is on average within 0.01 cm(-1), improving upon previous measurements.

The formation of the first monolayer of water molecules on bare dust grains is of primary importance to understand the growth of the icy mantles that cover dust in the interstellar medium. In this work, we explore experimentally the formation of water molecules from O(2) + D reaction on bare silicate surfaces that simulates the grains present in the diffuse interstellar clouds at visual extinctions (A(V) < 3 mag). For comparison, we also study the formation of water molecules on surfaces covered with amorphous water ice representing the dense clouds (A(V) ≥ 3 mag). Our studies focus on the formation of water molecules in the sub-monolayer and monolayer regimes using reflection absorption infrared spectroscopy and temperature-programmed desorption techniques. We provide the fractions of the products, such as D(2)O and D(2)O(2) molecules formed on three astrophysically relevant surfaces held at 10 K (amorphous olivine-type silicate, porous amorphous water ice, and nonporous amorphous water ice). Our results showed that the formation of D(2)O molecules occurs with an efficiency of about 55%-60% on nonporous amorphous water ice and about 18% on bare silicate grains surfaces. We explain the low efficiency of D(2)O water formation on the silicate surfaces by the desorption upon formation of certain products once the reaction occurs between O(2) and D atoms on the surface. A kinetic model taking into account the chemical desorption of newly formed water supports our conclusions.

The morphology of water ice in the interstellar medium is still an open question. Although accretion of gaseous water could not be the only possible origin of the observed icy mantles covering dust grains in cold molecular clouds, it is well known that water accreted from the gas phase on surfaces kept at 10 K forms ice films that exhibit a very high porosity. It is also known that in the dark clouds H(2) formation occurs on the icy surface of dust grains and that part of the energy (4.48 eV) released when adsorbed atoms react to form H(2) is deposited in the ice. The experimental study described in the present work focuses on how relevant changes of the ice morphology result from atomic hydrogen exposure and subsequent recombination. Using the temperature-programmed desorption (TPD) technique and a method of inversion analysis of TPD spectra, we show that there is an exponential decrease in the porosity of the amorphous water ice sample following D-atom irradiation. This decrease is inversely proportional to the thickness of the ice and has a value of ϕ(0) = 2 × 10(16) D-atoms cm(-2) per layer of H(2)O. We also use a model which confirms that the binding sites on the porous ice are destroyed regardless of their energy depth, and that the reduction of the porosity corresponds in fact to a reduction of the effective area. This reduction appears to be compatible with the fraction of D(2) formation energy transferred to the porous ice network. Under interstellar conditions, this effect is likely to be efficient and, together with other compaction processes, provides a good argument to believe that interstellar ice is amorphous and non-porous., (This journal is © the Owner Societies 2011)

Nuclear spin conversion (NSC) of ortho- to para-H(2) and para- to ortho-D(2) has been investigated on an amorphous solid water (ASW) surface at 10 K, in the presence of co-adsorbed O(2). The dynamics of the nuclear spin conversion could be revealed by combination of resonance enhanced multiphoton ionization spectroscopy (REMPI) with temperature programmed desorption (TPD) experiments. The conversion rates are consistent with a diffusion of molecular hydrogen inducing a nuclear spin conversion enhanced in the vicinity of molecular oxygen. The conversion times were found to increase with decreasing O(2) and H(2) coverage. Finally, on oxygen free ASW surface, the extremely long conversion characteristic times measured showed that such surface is not an efficient catalyst for NSC, in contradiction with hypothesis commonly made for interstellar medium.

Using the King and Wells method, we present experimental data on the dependence of the sticking of molecular hydrogen and deuterium on the beam temperature onto nonporous amorphous solid water ice surfaces of interstellar interest. A statistical model that explains the isotopic effect and the beam temperature behavior of our data is proposed. This model gives an understanding of the discrepancy between all known experimental results on the sticking of molecular hydrogen. Moreover, it is able to fit the theoretical results of Buch et al. [Astrophys. J. 379, 647 (1991)] on atomic hydrogen and deuterium. For astrophysical applications, an analytical formula for the sticking coefficients of H, D, H(2), D(2), and HD in the case of a gas phase at thermal equilibrium is also provided at the end of the article.

The desorption kinetics of D(2) from amorphous solid water (ASW) films have been studied by the temperature-programmed desorption (TPD) technique in the 10-30 K temperature range. Compact (and nonporous) films were grown at 120 K over a copper substrate. Ultra-thin porous films were additionally grown at 10 K over the compact base. The TPD spectra from compact and from up to 20 monolayers (ML) porous films were compared. The simulation of the TPD experimental traces provides the corresponding D(2) binding-energy distributions. As compared to the compact case, the binding-energy distribution found for the 10 ML porous film clearly extends to higher energies. To study the transition from compact to porous ice, porous films of intermediate thicknesses (<10 ML), including ultra-thin films (<1 ML), were grown over the compact substrate. The thermal D(2) desorption peak was found to shift to higher temperatures as the porous ice network was progressively formed. This behavior can be explained by the formation of more energetic binding sites related to porous films. TPD spectra were also modelled by using a combination of the two energy distributions, one associated to a bare compact ice and the other associated to a 10 ML porous ice film. This analysis reveals a very fast evolution of the binding-energy distribution towards that of porous ice. Our results show that few ML of additional porous film are sufficient to produce a sample for which the D(2) adsorption can be described by the energy distribution found for the 10 ML porous film. These experiments then provide evidence that the binding energy of D(2) on ASW ice is primarily governed by the topological and morphological disorder of the surface at molecular scale.

Molecular hydrogen interaction on water ice surfaces is a major process taking place in interstellar dense clouds. By coupling laser detection and classical thermal desorption spectroscopy, it is possible to study the effect of rotation of D(2) on adsorption on amorphous solid water ice surfaces. The desorption profiles of ortho- and para-D(2) are different. This difference is due to a shift in the adsorption energy distribution of the two lowest rotational states. Molecules in J''=1 rotational state are on average more strongly bound to the ice surface than those in J''=0 rotational state. This energy difference is estimated to be 1.4+/-0.3 meV. This value is in agreement with previous calculation and interpretation. The nonspherical wave function J'' =1 has an interaction with the asymmetric part of the adsorption potential and contributes positively in the binding energy.

Molecular and atomic interactions of hydrogen on dust grains covered with ice at low temperatures are key mechanisms for star formation and chemistry in dark interstellar clouds. We have experimentally studied the interaction of atomic and molecular deuterium on nonporous amorphous water ice surfaces between 8 and 30 K, in conditions compatible with an extrapolation to an astrophysical context. The adsorption energy of D(2) presents a wide distribution, as already observed on porous water ice surfaces. At low coverage, the sticking coefficient of D(2) increases linearly with the number of deuterium molecules already adsorbed on the surface. Recombination of atomic D occurs via a prompt reaction that releases molecules into the gas phase. Part of the newly formed molecules are in vibrationally excited states (v=1-7). The atomic recombination efficiency increases with the presence of D(2) molecules already adsorbed on the water ice, probably because these increase the sticking coefficient of the atoms, as in the case of incident D(2). We have measured the atomic recombination efficiency in the presence of already absorbed D(2), as it is expected to occur in the interstellar medium. The recombination efficiency decreases rapidly with increasing temperature and is zero at 13 K. This allows us to estimate an upper limit to the value of the atom adsorption energy E(a) approximately 29 meV, in agreement with previous calculations.

The gas-surface interaction of molecular hydrogen D2 with a thin film of porous amorphous solid water (ASW) grown at 10 K by slow vapor deposition has been studied by temperature-programmed-desorption (TPD) experiments. Molecular hydrogen diffuses rapidly into the porous network of the ice. The D2 desorption occurring between 10 and 30 K is considered here as a good probe of the effective surface of ASW interacting with the gas. The desorption kinetics have been systematically measured at various coverages. A careful analysis based on the Arrhenius plot method has provided the D2 binding energies as a function of the coverage. Asymmetric and broad distributions of binding energies were found, with a maximum population peaking at low energy. We propose a model for the desorption kinetics that assumes a complete thermal equilibrium of the molecules with the ice film. The sample is characterized by a distribution of adsorption sites that are filled according to a Fermi-Dirac statistic law. The TPD curves can be simulated and fitted to provide the parameters describing the distribution of the molecules as a function of their binding energy. This approach contributes to a correct description of the interaction of molecular hydrogen with the surface of possibly porous grain mantles in the interstellar medium.

In the incubation process of domestic avian eggs, the development of the embryo is mainly influenced by the physical microenvironment around the egg. Only small spatiotemporal deviations in the optimal incubator air temperature are allowed to optimize hatchability and hatchling quality. The temperature of the embryo depends on 3 factors: (1) the air temperature, (2) the exchange of heat between the egg and its microenvironment and (3) the time-variable heat production of the embryo. Theoretical estimates on the heat exchange between an egg and its physical microenvironment are approximated using equations that assume an approximate spherical shape for eggs. The objective of this research was to determine the heat transfer between the eggshell and its microenvironment and then compare this value to various theoretical estimates. By using experimental data, the overall and the convective heat transfer coefficients were determined as a function of heat production, air humidity, air speed, and air temperature. Heat transfer was not affected by air humidity but solely by air temperature, embryonic heat generation, and air speed and flow around eggs. Also, heat transfer in forced-air incubators occurs mainly by convective heat loss, which is dependent on the speed of airflow. A vertical airflow is more efficient than a horizontal airflow in transferring heat from the egg. We showed that describing an egg as a sphere underestimated convective heat transfer by 33% and was, therefore, too simplistic to accurately assess actual heat transfer from real eggs.

This work presents absorption and photofragment fluorescence spectra of water (H2O and D2O) simultaneously recorded at rotational resolution and at room temperature, by means of a synchrotron radiation source in the range 10.9-12 eV, covering the nd intense series from n=3 to 8. The Rydberg states observed are assigned in the light of the most advanced theoretical work available [M. S. Child, Philos. Trans. R. Soc. London, Ser. A 355, 1623 (1997)], and by reference to the stretching and bending mode progressions. Comparison between absorption and fluorescence spectra is shown to reveal a fast predissociation mechanism involving the linear 3pb2 1B2 state, and permits the identification of its (0,14,0) vibrational level observed in the absorption spectra.

The comparison of two spectral lines of almost identical wavelength can be made by recording simultaneously the output of a single spectrometer fed by two sources. The two channels are separated either through time-sharing or through modulation at two different frequencies and synchronous detection. Wavelength shifts as small as 1 mA have been determined for a measured shift/width ratio less than 0.05 on cesium absorption lines broadened by rare gases.