Yasuhiro Oba

FORMATION OF COMPACT AMORPHOUS H2O ICE BY CODEPOSITION OF HYDROGEN ATOMS WITH OXYGEN MOLECULES ON GRAIN SURFACES

Formation of H2O molecules through the codeposition of oxygen molecules and hydrogen atoms is examined in situ using IR spectroscopy at 10-40 K under various O2 and H fluxes. It is found that H2O and H2O2 are continuously formed by reaction, even at 40 K. The H2O ice formed is amorphous, but has a compact (not microporous) structure compared to vapor-deposited amorphous H2O ice, because dangling OH bonds are not observed in the IR spectrum. This is consistent with astronomical observations in molecular clouds and theoretical predictions, which suggest that hydrogenation of O2 is one of the potential routes for reproducing these IR spectral characteristics. The composition of the ice formed by codeposition varies with the O2/H ratio and temperature. Although no data are available at present for the H2O/H2O2 ratio of ice in molecular clouds, this study suggests that hydrogenation of O2 has a potential to yield a H2O/H2O2 ratio of 5 or more in molecular clouds.

EXPERIMENTAL STUDY OF CO2 FORMATION BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES

Surface reactions between carbon monoxide and non-energetic hydroxyl radicals were carried out at 10 K and 20 K in order to investigate possible reaction pathways to yield carbon dioxide in dense molecular clouds. Hydroxyl radicals, produced by dissociating water molecules in microwave-induced plasma, were cooled down to 100 K prior to the introduction of CO. The abundances of species were monitored in situ using a Fourier transform infrared spectrometer. Formation of CO2 was clearly observed, even at 10 K, suggesting that reactions of CO with OH proceed with little or no activation barrier. The present results indicate that CO2 formation, due to reactions between CO and OH, occurs in tandem with H2O formation, and this may lead to the formation of CO2 ice in polar environments, as typically observed in molecular clouds.

FORMATION OF CARBONIC ACID (H2CO3) BY SURFACE REACTIONS OF NON-ENERGETIC OH RADICALS WITH CO MOLECULES AT LOW TEMPERATURES

We present the experimental results of carbonic acid (H2CO3) formation through surface reactions of CO molecules with non-energetic hydroxyl (OH) radicals at 10-40 K. The formation of H2CO3 was clearly identified both in the IR spectra and in the thermally programmed desorption mass spectra. The H2CO3 yield was rather high, amounting to approximately 40%-70% relative to that of CO2 formed by the reaction of CO with OH. The structure of H2CO3 formed by reactions of CO with OH may differ from that formed by energetic processes such as UV irradiation, ion irradiation, and electron irradiation of H2O/CO2 binary ices. In this paper, we envisage some of the possible roles H2CO3 may have in the interstellar medium, such as enriching grain mantles of new molecules via acid-base reactions with basic species and contributing to the formation of the unidentified band at 6.8 μm; we suggest possible reasons for its non-detection yet and discuss the restoration of carbonic acid molecules in the gas phase.

Direct Evidence for Ammonium Ion Formation in Ice through Ultraviolet-induced Acid-Base Reaction of NH3 with H3O+

We present direct evidence for ammonium ion (NH4 +) formation through ultraviolet (UV) photolysis of NH3-H2O mixture ice that does not contain acids. NH4 + forms by the reaction of NH3 with protonic defects (H3O+) in the UV-photolyzed ice. Our observations may explain the deficient counter-anions in interstellar ice relative to the abundance of NH4 +. Also, H3O+ may play an important role in the acid-base chemistry of interstellar ice in UV-irradiating environments. IR absorption results suggest that NH4 + is a potential contributor to the interstellar 6.85 μm band but is not a dominant component.

Reaction kinetics and isotope effect of water formation by the surface reaction of solid H2O2 with H atoms at low temperatures

We performed laboratory experiments on the formation of water and its isotopologues by surface reactions of hydrogen peroxide (H2O2) with hydrogen (H) atoms and their deuterated counterparts (D2O2, D) at 10-30 K. High-purity H2O2 (> 95%) was prepared in situ by the codeposition of molecular oxygen and H atoms at relatively high temperatures (45-50 K). We determined that the high-purity H2O2 solid reacts with both H and deuterium (D) atoms at 10-30 K despite the large activation barriers (-2000 K). Moreover, the reaction rate for H atoms is approximately 45 times faster than that for D atoms at 15 K. Thus, the observed large isotope effect indicates that these reactions occurred through quantum tunneling. We propose that the observed HDO/H2O ratio in molecular clouds might be a good tool for the estimation of the atomic D/H ratio in those environments.

DEUTERIUM FRACTIONATION DURING AMINO ACID FORMATION BY PHOTOLYSIS OF INTERSTELLAR ICE ANALOGS CONTAINING DEUTERATED METHANOL

Deuterium (D) atoms in interstellar deuterated methanol might be distributed into complex organic molecules through molecular evolution by photochemical reactions in interstellar grains. In this study, we use a state-of-the-art high-resolution mass spectrometer coupled with a high-performance liquid chromatography system to quantitatively analyze amino acids and their deuterated isotopologues formed by the photolysis of interstellar ice analogs containing singly deuterated methanol CH2DOH at 10 K. Five amino acids (glycine, α-alanine, β-alanine, sarcosine, and serine) and their deuterated isotopologues whose D atoms are bound to carbon atoms are detected in organic residues formed by photolysis followed by warming up to room temperature. The abundances of singly deuterated amino acids are in the range of 0.3–1.1 relative to each nondeuterated counterpart, and the relative abundances of doubly and triply deuterated species decrease with an increasing number of D atoms in a molecule. The abundances of amino acids increase by a factor of more than five upon the hydrolysis of the organic residues, leading to decreases in the relative abundances of deuterated species for α-alanine and β-alanine. On the other hand, the relative abundances of the deuterated isotopologues of the other three amino acids did not decrease upon hydrolysis, indicating different formation mechanisms of these two groups upon hydrolysis. The present study facilitates both qualitative and quantitative evaluations of D fractionation during molecular evolution in the interstellar medium.

Nonenergetic reactions between atomic hydrogen and molecules on interstellar grain surfaces

Reactions of atomic hydrogen with CO and O2 on amorphous solid water (ASW), relevant to chemical evolution on cosmic ice dust, were experimentally investigated at around 10 K. Successive addition of hydrogen atoms to CO and O2 produces H2CO, CH3OH, and H2O2, H2O, respectively. At such low temperatures, some of hydrogen additions such as H + CO → HCO proceed via tunneling reactions rather than thermally-activated reactions. Effective reaction rates and isotope effect of the tunneling reactions to produce HCO and H2O were measured. The surface of ASW was found to enhance the effective rate of hydrogen addition to CO at relatively higher temperatures, namely around 20 K.

An infrared measurement of chemical desorption from interstellar ice analogues

In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular release mechanism almost 50 years ago1. Chemical desorption can, in principle, take place at any temperature, even below the thermal desorption temperature. Therefore, astrochemical network models commonly include this process2,3. Although there have been a few previous experimental efforts4–6, no infrared measurement of the surface (which has a strong advantage to quantify chemical desorption) has been performed. Here, we report the first infrared in situ measurement of chemical desorption during the reactions H + H2S → HS + H2 (reaction 1) and HS + H → H2S (reaction 2), which are key to interstellar sulphur chemistry2,3. The present study clearly demonstrates that chemical desorption is a more efficient process for releasing H2S into the gas phase than was previously believed. The obtained effective cross-section for chemical desorption indicates that the chemical desorption rate exceeds the photodesorption rate in typical interstellar environments.The efficiency of the chemical desorption caused by the reactions between H2S, HS and H on an icy grain surface analogue has been quantified by means of in situ infrared measurements of the surface, providing valuable information for understanding non-thermal desorption processes.

Liquid-like behavior of UV-irradiated interstellar ice analog at low temperatures

UV-irradiated interstellar ice analog behaves like a liquid at 50 to 150 kelvin, below its crystallization temperature. Interstellar ice is believed to be a cradle of complex organic compounds, commonly found within icy comets and interstellar clouds, in association with ultraviolet (UV) irradiation and subsequent warming. We found that UV-irradiated amorphous ices composed of H2O, CH3OH, and NH3 and of pure H2O behave like liquids over the temperature ranges of 65 to 150 kelvin and 50 to 140 kelvin, respectively. This low-viscosity liquid-like ice may enhance the formation of organic compounds including prebiotic molecules and the accretion of icy dust to form icy planetesimals under certain interstellar conditions.