Absence of molecular mobility on nano-second time scales in amorphous ice phases

High-resolution neutron backscattering techniques are exploited to study the elastic and quasi-elastic response of the high-density amorphous (HDA), the low-density amorphous (LDA) and the crystalline ice Ic upon temperature changes. Within the temperature ranges of their structural stability (HDA at T > 80 K, LDA at T > 135 K, ice Ic at T < 200 K) the Debye-Waller factors and mean-square displacements characterise all states as harmonic solids. During the transformations HDA->LDA (T ~ 100 K), LDA->Ic (T ~ 150K) and the supposed glass transition with Tg ~ 135 K no relaxation processes can be detected on a time scale t < 4 ns. It can be concluded from coherent scattering measurements (D_2O) that LDA starts to recrystallise into ice Ic at T ~ 135 K, i.e. at the supposed Tg. In the framework of the Debye model of harmonic solids HDA reveals the highest Debye temperature among the studied ice phases, which is in full agreement with the lowest Debye level in the generalised density of states derived from time-of-flight neutron scattering experiments. The elastic results at low T indicate the presence of an excess of modes in HDA, which do not obey the Bose statistics

A Search for Hydroxylamine (NH2OH) toward Select Astronomical Sources

Observations of 14 rotational transitions of hydroxylamine (NH2OH) using the NRAO 12 m Telescope on Kitt Peak are reported towards IRC+10216, Orion KL, Orion S, Sgr B2(N), Sgr B2(OH), W3IRS5, and W51M. Although recent models suggest the presence of NH2OH in high abundance, these observations resulted in non-detection. Upper limits are calculated to be as much as six orders of magnitude lower than predicted by models. Possible explanations for the lower than expected abundance are explored.Comment: 18 pages, 3 figures, 3 table

A Search for Hydroxylamine (NH_2OH) toward Select Astronomical Sources

Observations of 14 rotational transitions of hydroxylamine (NH_2OH) using the NRAO 12 m telescope on Kitt Peak are reported toward IRC+10216, Orion KL, Orion S, Sgr B2(N), Sgr B2(OH), W3IRS5, and W51M. Although recent models suggest the presence of NH_2OH in high abundance, these observations resulted in non-detection. Upper limits are calculated to be as much as six orders of magnitude lower than those predicted by models. Possible explanations for the lower-than-expected abundance are explored

Structure and Dynamics of Superconducting NaxCoO(2) Hydrate and Its Unhydrated Analog

Neutron scattering has been used to investigate the crystal structure and lattice dynamics of superconducting Na0.3CoO2 1.4(H/D)2O, and the parent Na0.3CoO2 material. The structure of Na0.3CoO2 consists of alternate layers of CoO2 and Na and is the same as the structure at higher Na concentrations. For the superconductor, the water forms two additional layers between the Na and CoO2, increasing the c-axis lattice parameter of the hexagonal P63/mmc space group from 11.16 A to 19.5 A. The Na ions are found to occupy a different configuration from the parent compound, while the water forms a structure that replicates the structure of ice. Both types of sites are only partially occupied. The CoO2 layer in these structures is robust, on the other hand, and we find a strong inverse correlation between the CoO2 layer thickness and the superconducting transition temperature (TC increases with decreasing thickness). The phonon density-of-states for Na0.3CoO2 exhibits distinct acoustic and optic bands, with a high-energy cutoff of ~100 meV. The lattice dynamical scattering for the superconductor is dominated by the hydrogen modes, with librational and bending modes that are quite similar to ice, supporting the structural model that the water intercalates and forms ice-like layers in the superconductor.Comment: 14 pages, 7 figures, Phys. Rev. B (in press). Minor changes + two figures removed as requested by refere

Hydrogen bonding characterization in water and small molecules

The prototypical Hydrogen bond in water dimer and Hydrogen bonds in the protonated water dimer, in other small molecules, in water cyclic clusters, and in ice, covering a wide range of bond strengths, are theoretically investigated by first-principles calculations based on the Density Functional Theory, considering a standard Generalized Gradient Approximation functional but also, for the water dimer, hybrid and van-der-Waals corrected functionals. We compute structural, energetic, and electrostatic (induced molecular dipole moments) properties. In particular, Hydrogen bonds are characterized in terms of differential electron densities distributions and profiles, and of the shifts of the centres of Maximally localized Wannier Functions. The information from the latter quantities can be conveyed into a single geometric bonding parameter that appears to be correlated to the Mayer bond order parameter and can be taken as an estimate of the covalent contribution to the Hydrogen bond. By considering the cyclic water hexamer and the hexagonal phase of ice we also elucidate the importance of cooperative/anticooperative effects in Hydrogen-bonding formation.Comment: 11 figure

The genealogical tree of ethanol: gas-phase formation of glycolaldehyde, acetic acid and formic acid

Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesised is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this article, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of ten, which might imply a yet incomplete reaction network

Protonated CO2 in massive star-forming clumps

Interstellar CO2 is an important reservoir of carbon and oxygen, and one of the major constituents of the icy mantles of dust grains, but it is not observable directly in the cold gas because has no permanent dipole moment. Its protonated form, HOCO+, is believed to be a good proxy for gaseous CO2. However, it has been detected in only a few star-forming regions so far, so that its interstellar chemistry is not well understood. We present new detections of HOCO+ lines in 11 high-mass star-forming clumps. Our observations increase by more than three times the number of detections in star-forming regions so far. We have derived beam-averaged abundances relative to H2 in between 0.3 and 3.8 x 10^{-11}. We have compared these values with the abundances of H13CO+, a possible gas-phase precursor of HOCO+, and CH3OH, a product of surface chemistry. We have found a positive correlation with H13CO+, while with CH3OH there is no correlation. We suggest that the gas-phase formation route starting from HCO+ plays an important role in the formation of HOCO+, perhaps more relevant than protonation of CO2 (upon evaporation of this latter from icy dust mantles).Comment: 5 pages, 4 figures, 1 table, accepted for publication in MNRA

A study of methyl formate in astrochemical environments

Several complex organic molecules are routinely detected in high abundances towards hot cores and hot corinos. For many of them, their paths of formation in space are uncertain, as gas phase reactions alone seem to be insufficient. In this paper, we investigate a possible solid-phase route of formation for methyl formate (HCOOCH3). We use a chemical model updated with recent results from an experiment where simulated grain surfaces were irradiated with 200 keV protons at 16 K, to simulate the effects of cosmic ray irradiation on grain surfaces. We find that this model may be sufficient to reproduce the observed methyl formate in dark clouds, but not that found in hot cores and corinos.Comment: 6 pages, 2 figures, 2 tables Accepted by MNRA