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

Smart cities: A literature review and business network approach discussion on the management of organisations

Purpose: The smart city idea refers to new ways of organising city functions and urban life, which are believed to move production and consumption from global to local, manufacturing from competitive to collaborative, and business from a shareholder to a multiple-stakeholder point of view. Most previous research has focussed on the societal level of smart cities, while less seems to be known about the management of business as part of smart cities. The purpose of this paper is to present a literature review on the state of the art of management research on smart cities. The following research question is addressed: How has previous research captured the management of organisations in smart cities? Design/methodology/approach: A literature review using the search term “smart city/cities” in research on business, management, and operational management was conducted for the purpose of capturing previous research. Findings were coded based on main ideas, central concepts, and theories, thematic content of the articles related to the main ideas underpinning smart cities (digitalization, urbanisation, and sustainability as antecedents, and local, collaborative and multiple-stakeholder manufacturing as indicators), and units of analysis. Findings: The paper points to how most studies on the management of organisations as part of smart cities focus on sustainability and how digitalisation enables new businesses. Collaborative efforts are emphasised and the theoretical framing is fragmented. Issues related to the organising of business is also not problematised and the business network approach could, as discussed in the paper, provide valuable insights related to the collaborative efforts of organisations and the multiple-stakeholder perspective. Originality/value: The paper is the first to capture and present an overview of previous research on the management of business as part of smart cities. Research on smart cities has focussed on the policy and societal levels, and so far there is a lack of problematisation on how organisations may act, and potentially change their way of acting, should smart cities become a reality

Laboratory H2O:CO2 ice desorption data: entrapment dependencies and its parameterization with an extended three-phase model

Ice desorption affects the evolution of the gas-phase chemistry during the protostellar stage, and also determines the chemical composition of comets forming in circumstellar disks. From observations, most volatile species are found in H2O-dominated ices. The aim of this study is first to experimentally determine how entrapment of volatiles in H2O ice depends on ice thickness, mixture ratio and heating rate, and second, to introduce an extended three-phase model (gas, ice surface and ice mantle) to describe ice mixture desorption with a minimum number of free parameters. Thermal H2O:CO2 ice desorption is investigated in temperature programmed desorption experiments of thin (10 - 40 ML) ice mixtures under ultra-high vacuum conditions. Desorption is simultaneously monitored by mass spectrometry and reflection-absorption infrared spectroscopy. The H2O:CO2 experiments are complemented with selected H2O:CO, and H2O:CO2:CO experiments. The results are modeled with rate equations that connect the gas, ice surface and ice mantle phases through surface desorption and mantle-surface diffusion. The fraction of trapped CO2 increases with ice thickness (10 - 32 ML) and H2O:CO2 mixing ratio (5:1 - 10:1), but not with one order of magnitude different heating rates. The fraction of trapped CO2 is 44 - 84 % with respect to the initial CO2 content for the investigated experimental conditions. This is reproduced quantitatively by the extended three-phase model that is introduced here. The H2O:CO and H2O:CO2:CO experiments are consistent with the H2O:CO2 desorption trends, suggesting that the model can be used for other ice species found in the interstellar medium to significantly improve the parameterization of ice desorption.Comment: 12 pages, 9 figures, published in A&

DCO+^+, DCN and N2_2D+^+ reveal three different deuteration regimes in the disk around the Herbig Ae star HD163296

The formation pathways of deuterated species trace different regions of protoplanetary disks and may shed light into their physical structure. We aim to constrain the radial extent of main deuterated species; we are particularly interested in spatially characterizing the high and low temperature pathways for enhancing deuteration of these species. We observed the disk surrounding the Herbig Ae star HD 163296 using ALMA in Band 6 and obtained resolved spectral imaging data of DCO$^+$ ($J$=3-2), DCN ($J$=3-2) and N$_2$D$^+$ ($J$=3-2). We model the radial emission profiles of DCO$^+$, DCN and N$_2$D$^+$, assuming their emission is optically thin, using a parametric model of their abundances and radial excitation temperature estimates. DCO$^+$ can be described by a three-region model, with constant-abundance rings centered at 70 AU, 150 AU and 260 AU. The DCN radial profile peaks at about ~60 AU and N$_2$D$^+$ is seen in a ring at ~160 AU. Simple models of both molecules using constant abundances reproduce the data. Assuming reasonable average excitation temperatures for the whole disk, their disk-averaged column densities (and deuterium fractionation ratios) are 1.6-2.6$\times 10^{12}$ cm$^{-2}$ (0.04-0.07), 2.9-5.2$\times 10^{12}$ cm$^{-2}$ ($\sim$0.02) and 1.6-2.5 $\times 10^{11}$ cm$^{-2}$ (0.34-0.45) for DCO$^+$, DCN and N$_2$D$^+$, respectively. Our simple best-fit models show a correlation between the radial location of the first two rings in DCO$^+$ and the DCN and N$_2$D$^+$ abundance distributions that can be interpreted as the high and low temperature deuteration pathways regimes. The origin of the third DCO$^+$ ring at 260 AU is unknown but may be due to a local decrease of ultraviolet opacity allowing the photodesorption of CO or due to thermal desorption of CO as a consequence of radial drift and settlement of dust grains

Quantification of segregation dynamics in ice mixtures

(Abridged) The observed presence of pure CO2 ice in protostellar envelopes is attributed to thermally induced ice segregation, but a lack of quantitative experimental data has prevented its use as a temperature probe. Quantitative segregation studies are also needed to characterize diffusion in ices, which underpins all ice dynamics and ice chemistry. This study aims to quantify the segregation mechanism and barriers in different H2O:CO2 and H2O:CO ice mixtures covering a range of astrophysically relevant ice thicknesses and mixture ratios. The ices are deposited at 16-50 K under (ultra-)high vacuum conditions. Segregation is then monitored at 23-70 K as a function of time, through infrared spectroscopy. Thin (8-37 ML) H2O:CO2/CO ice mixtures segregate sequentially through surface processes, followed by an order of magnitude slower bulk diffusion. Thicker ices (>100 ML) segregate through a fast bulk process. The thick ices must therefore be either more porous or segregate through a different mechanism, e.g. a phase transition. The segregation dynamics of thin ices are reproduced qualitatively in Monte Carlo simulations of surface hopping and pair swapping. The experimentally determined surface-segregation rates for all mixture ratios follow the Ahrrenius law with a barrier of 1080[190] K for H2O:CO2 and 300[100] K for H2O:CO mixtures. During low-mass star formation H2O:CO2 segregation will be important already at 30[5] K. Both surface and bulk segregation is proposed to be a general feature of ice mixtures when the average bond strengths of the mixture constituents in pure ice exceeds the average bond strength in the ice mixture.Comment: Accepted for publication in A&A. 25 pages, including 13 figure

Increased H2_2CO production in the outer disk around HD 163296

Three formaldehyde lines were observed (H$_2$CO 3$_{03}$--2$_{02}$, H$_2$CO 3$_{22}$--2$_{21}$, and H$_2$CO 3$_{21}$--2$_{20}$) in the protoplanetary disk around the Herbig Ae star HD 163296 with ALMA at 0.5 arcsecond (60 AU) spatial resolution. H$_2$CO 3$_{03}$--2$_{02}$ was readily detected via imaging, while the weaker H$_2$CO 3$_{22}$--2$_{21}$ and H$_2$CO 3$_{21}$--2$_{20}$ lines required matched filter analysis to detect. H$_2$CO is present throughout most of the gaseous disk, extending out to 550 AU. An apparent 50 AU inner radius of the H$_2$CO emission is likely caused by an optically thick dust continuum. The H$_2$CO radial intensity profile shows a peak at 100 AU and a secondary bump at around 300 AU, suggesting increased production in the outer disk. Different parameterizations of the H$_2$CO abundance were compared to the observed visibilities with $\chi^2$ minimization, using either a characteristic temperature, a characteristic radius or a radial power law index to describe the H$_2$CO chemistry. Similar models were applied to ALMA Science Verification data of C$^{18}$O. In all modeling scenarios, fits to the H$_2$CO data show an increased abundance in the outer disk. The overall best-fit H$_2$CO model shows a factor of two enhancement beyond a radius of 270$\pm$20 AU, with an inner abundance of $2\!-\!5 \times 10^{-12}$. The H$_2$CO emitting region has a lower limit on the kinetic temperature of $T > 20$ K. The C$^{18}$O modeling suggests an order of magnitude depletion in the outer disk and an abundance of $4\!-\!12 \times 10^{-8}$ in the inner disk. The increase in H$_2$CO outer disk emission could be a result of hydrogenation of CO ices on dust grains that are then sublimated via thermal desorption or UV photodesorption, or more efficient gas-phase production beyond about 300 AU if CO is photodisocciated in this region

The cometary composition of a protoplanetary disk as revealed by complex cyanides

Observations of comets and asteroids show that the Solar Nebula that spawned our planetary system was rich in water and organic molecules. Bombardment brought these organics to the young Earth's surface, seeding its early chemistry. Unlike asteroids, comets preserve a nearly pristine record of the Solar Nebula composition. The presence of cyanides in comets, including 0.01% of methyl cyanide (CH3CN) with respect to water, is of special interest because of the importance of C-N bonds for abiotic amino acid synthesis. Comet-like compositions of simple and complex volatiles are found in protostars, and can be readily explained by a combination of gas-phase chemistry to form e.g. HCN and an active ice-phase chemistry on grain surfaces that advances complexity[3]. Simple volatiles, including water and HCN, have been detected previously in Solar Nebula analogues - protoplanetary disks around young stars - indicating that they survive disk formation or are reformed in situ. It has been hitherto unclear whether the same holds for more complex organic molecules outside of the Solar Nebula, since recent observations show a dramatic change in the chemistry at the boundary between nascent envelopes and young disks due to accretion shocks[8]. Here we report the detection of CH3CN (and HCN and HC3N) in the protoplanetary disk around the young star MWC 480. We find abundance ratios of these N-bearing organics in the gas-phase similar to comets, which suggests an even higher relative abundance of complex cyanides in the disk ice. This implies that complex organics accompany simpler volatiles in protoplanetary disks, and that the rich organic chemistry of the Solar Nebula was not unique.Comment: Definitive version of the manuscript is published in Nature, 520, 7546, 198, 2015. This is the author's versio

Water formation at low temperatures by surface O2 hydrogenation II: the reaction network

Water is abundantly present in the Universe. It is the main component of interstellar ice mantles and a key ingredient for life. Water in space is mainly formed through surface reactions. Three formation routes have been proposed in the past: hydrogenation of surface O, O2, and O3. In a previous paper [Ioppolo et al., Astrophys. J., 2008, 686, 1474] we discussed an unexpected non-standard zeroth-order H2O2 production behaviour in O2 hydrogenation experiments, which suggests that the proposed reaction network is not complete, and that the reaction channels are probably more interconnected than previously thought. In this paper we aim to derive the full reaction scheme for O2 surface hydrogenation and to constrain the rates of the individual reactions. This is achieved through simultaneous H-atom and O2 deposition under ultra-high vacuum conditions for astronomically relevant temperatures. Different H/O2 ratios are used to trace different stages in the hydrogenation network. The chemical changes in the forming ice are followed by means of reflection absorption infrared spectroscopy (RAIRS). New reaction paths are revealed as compared to previous experiments. Several reaction steps prove to be much more efficient (H + O2) or less efficient (H + OH and H2 + OH) than originally thought. These are the main conclusions of this work and the extended network concluded here will have profound implications for models that describe the formation of water in space.Comment: 1 page, 1 figur