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Harold Linnartz

Publications and source records attributed to Harold Linnartz.

At least 55 records · Page 3Linked to original sources
arXiv2017

Deuterium enrichment of ammonia produced by surface N+H/D addition reactions at low temperature

The surface formation of NH3 and its deuterated isotopologues - NH2D, NHD2, and ND3 - is investigated at low temperatures through the simultaneous addition of hydrogen and deuterium atoms to nitrogen atoms in CO-rich interstellar ice analogues. The formation of all four ammonia isotopologues is only observed up to 15 K, and drops below the detection limit for higher temperatures. Differences between hydrogenation and deuteration yields result in a clear deviation from a statistical distribution in favour of deuterium enriched species. The data analysis suggests that this is due to a higher sticking probability of D atoms to the cold surface, a property that may generally apply to molecules that are formed in low temperature surface reactions. The results found here are used to interpret ammonia deuterium fractionation as observed in pre-protostellar cores.

astro-ph.GA↗
arXiv2017

Low Temperature Surface Formation of NH3 and HNCO: hydrogenation of nitrogen atoms in CO-rich interstellar ice analogues

Solid state astrochemical reaction pathways have the potential to link the formation of small nitrogen-bearing species, like NH3 and HNCO, and prebiotic molecules, specifically amino acids. To date, the chemical origin of such small nitrogen containing species is still not well understood, despite the fact that ammonia is an abundant constituent of interstellar ices toward young stellar objects and quiescent molecular clouds. This is mainly because of the lack of dedicated laboratory studies. The aim of the present work is to experimentally investigate the formation routes of NH3 and HNCO through non-energetic surface reactions in interstellar ice analogues under fully controlled laboratory conditions and at astrochemically relevant temperatures. This study focuses on the formation of NH3 and HNCO in CO-rich (non-polar) interstellar ices that simulate the CO freeze-out stage in dark interstellar cloud regions, well before thermal and energetic processing start to become relevant. We demonstrate and discuss the surface formation of solid HNCO through the interaction of CO molecules with NH radicals - one of the intermediates in the formation of solid NH3 upon sequential hydrogenation of N atoms. The importance of HNCO for astrobiology is discussed.

astro-ph.GA↗
arXiv2017

Experimental evidence for Glycolaldehyde and Ethylene Glycol formation by surface hydrogenation of CO molecules under dense molecular cloud conditions

This study focuses on the formation of two molecules of astrobiological importance - glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH) - by surface hydrogenation of CO molecules. Our experiments aim at simulating the CO freeze-out stage in interstellar dark cloud regions, well before thermal and energetic processing become dominant. It is shown that along with the formation of H2CO and CH3OH - two well established products of CO hydrogenation - also molecules with more than one carbon atom form. The key step in this process is believed to be the recombination of two HCO radicals followed by the formation of a C-C bond. The experimentally established reaction pathways are implemented into a continuous-time random-walk Monte Carlo model, previously used to model the formation of CH3OH on astrochemical time-scales, to study their impact on the solid-state abundances in dense interstellar clouds of glycolaldehyde and ethylene glycol.

astro-ph.GA↗
arXiv2017

Simultaneous Hydrogenation and UV-photolysis Experiments of NO in CO-rich Interstellar Ice Analogues; linking HNCO, OCN-, NH2CHO and NH2OH

The laboratory work presented here, simulates the chemistry on icy dust grains as typical for the 'CO freeze-out stage' in dark molecular clouds. It differs from previous studies in that solid-state hydrogenation and vacuum UV-photoprocessing are applied simultaneously to co-depositing molecules. In parallel, the reactions at play are described for fully characterized laboratory conditions. The focus is on the formation of molecules containing both carbon and nitrogen atoms, starting with NO in CO-, H2CO-, and CH3OH-rich ices at 13 K. The experiments yield three important conclusions. 1. Without UV-processing hydroxylamine (NH2OH) is formed, as reported previously. 2. With UV-processing (energetic) NH2 is formed through photodissociation of NH2OH. This radical is key in the formation of species with an N-C bond. 3. The formation of three N-C bearing species, HNCO, OCN- and NH2CHO is observed. The experiments put a clear chemical link between these species; OCN- is found to be a direct derivative of HNCO and the latter is shown to have the same precursor as formamide (NH2CHO). Moreover, the addition of VUV competing channels decreases the amount of NO molecules converted into NH2OH by at least one order of magnitude. Consequently, this decrease in NH2OH formation yield directly influences the amount of NO molecules that can be converted into HNCO, OCN- and NH2CHO.

astro-ph.GA↗
arXiv2016

Importance of tunneling in H-abstraction reactions by OH radicals: The case of CH4 + OH studied through isotope-substituted analogs

We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD -> CH3 + HDO and CD4 + OH -> CD3 + HDO. The experimental study shows that the solid-state reaction rate R(CH4 + OD) is higher than R(CD4 + OH) at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. From the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (k(CH4 + OD)) is approximately ten times faster than D-abstraction (k(CD4 + OH)) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion.

astro-ph.GA↗
arXiv2016

A Spectroscopic Survey of Electronic Transitions of C$_6$H, $^{13}$C$_6$H, and C$_6$D

Electronic spectra of C$_6$H are measured in the $18\,950-21\,100$ cm$^{-1}$ domain using cavity ring-down spectroscopy of a supersonically expanding hydrocarbon plasma. In total, 19 (sub)bands of C$_6$H are presented, all probing the vibrational manifold of the B$^2Π$ electronically excited state. The assignments are guided by electronic spectra available from matrix isolation work, isotopic substitution experiments (yielding also spectra for $^{13}$C$_6$H and C$_6$D), predictions from ab initio calculations as well as rotational fitting and vibrational contour simulations using the available ground state parameters as obtained from microwave experiments. Besides the $0_0^0$ origin band, three non-degenerate stretching vibrations along the linear backbone of the C$_6$H molecule are assigned: the $ν_6$ mode associated with the C-C bond vibration and the $ν_4$ and $ν_3$ modes associated with C$\equiv$C triple bonds. For the two lowest $ν_{11}$ and $ν_{10}$ bending modes, a Renner-Teller analysis is performed identifying the $μ^2Σ$($ν_{11}$) and both $μ^2Σ$($ν_{10}$) and $κ^2Σ$($ν_{10}$) components. In addition, two higher lying bending modes are observed, which are tentatively assigned as $μ^2Σ$($ν_9$) and $μ^2Σ$($ν_8$) levels. In the excitation region below the first non-degenerate vibration ($ν_6$), some $^2Π-^{2}Π$ transitions are observed that are assigned as even combination modes of low-lying bending vibrations. The same holds for a $^2Π-^{2}Π$ transition found above the $ν_6$ level. From these spectroscopic data and the vibronic analysis a comprehensive energy level diagram for the B$^2Π$ state of C$_6$H is derived and presented.

physics.chem-ph↗
arXiv2016

UV photodesorption of methanol in pure and CO-rich ices: desorption rates of the intact molecule and of the photofragments

Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH$_3$OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH$_3$, OH, H$_2$CO and CH$_3$O/CH$_2$OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH$_3$O, therefore opening new gas phase chemical routes for the formation of complex molecules.

astro-ph.GA↗
arXiv2015

Atom addition reactions in interstellar ice analogues

This review paper summarizes the state-of-the-art in laboratory based interstellar ice chemistry. The focus is on atom addition reactions, illustrating how water, carbon dioxide and methanol can form in the solid state at astronomically relevant temperatures, and also the formation of more complex species such as hydroxylamine, an important prebiotic molecule, and glycolaldehyde, the smallest sugar, is discussed. These reactions are particularly relevant during the dark ages of star and planet formation, i.e., when the role of UV light is restricted. A quantitative characterization of such processes is only possible through dedicated laboratory studies, i.e., under full control of a large set of parameters such as temperature, atom-flux, and ice morphology. The resulting numbers, physical and chemical constants, e.g., barrier heights, reaction rates and branching ratios, provide information on the molecular processes at work and are needed as input for astrochemical models, in order to bridge the timescales typical for a laboratory setting to those needed to understand the evolutionary stages of the interstellar medium. Details of the experiments as well as the astrochemical impact of the results are discussed.

astro-ph.GA↗
arXiv2015

Laboratory Photo-chemistry of PAHs: Ionization versus Fragmentation

Interstellar polycyclic aromatic hydrocarbons (PAHs) are expected to be strongly processed by vacuum ultraviolet photons. Here, we report experimental studies on the ionization and fragmentation of coronene (C24H12), ovalene (C32H14) and hexa-peri-hexabenzocoronene (HBC; C42H18) cations by exposure to synchrotron radiation in the range of 8--40 eV. The results show that for small PAH cations such as coronene, fragmentation (H-loss) is more important than ionization. However, as the size increases, ionization becomes more and more important and for the HBC cation, ionization dominates. These results are discussed and it is concluded that, for large PAHs, fragmentation only becomes important when the photon energy has reached the highest ionization potential accessible. This implies that PAHs are even more photo-stable than previously thought. The implications of this experimental study for the photo-chemical evolution of PAHs in the interstellar medium are briefly discussed.

astro-ph.IM↗
arXiv2015

Thermal H/D exchange in polar ice - deuteron scrambling in space

We have investigated the thermally induced proton/deuteron exchange in mixed amorphous H$_2$O:D$_2$O ices by monitoring the change in intensity of characteristic vibrational bending modes of H$_2$O, HDO, and D$_2$O with time and as function of temperature. The experiments have been performed using an ultra-high vacuum setup equipped with an infrared spectrometer that is used to investigate the spectral evolution of homogeneously mixed ice upon co-deposition in thin films, for temperatures in the 90 to 140 K domain. With this non-energetic detection method we find a significantly lower activation energy for H/D exchange -- $3840 \pm 125$ K -- than previously reported. Very likely this is due to the amorphous nature of the interstellar ice analogues involved. This provides reactive timescales ($τ<10^4$ years at $T$ $>70$ K) fast enough for the process to be important in interstellar environments. Consequently, an astronomical detection of D$_2$O will be even more challenging because of its potential to react with H$_2$O to form HDO. Furthermore, additional experiments, along with previous studies, show that proton/deuteron swapping also occurs in ice mixtures of water with other hydrogen bonded molecules, in particular on the OH and NH moieties. We conclude that H/D exchange in ices is a more general process that should be incorporated into ice models that are applied to protoplanetary disks or to simulate the warming up of cometary ices in their passage of the perihelion, to examine the extent of its influence on the final deuteron over hydrogen ratio.

astro-ph.GA↗
arXiv2015

The B$^2Π-$X$^2Π$ electronic origin band of $^{13}$C$_6$H

The rotationally resolved spectrum of the B$^2Π-$X$^2Π$ electronic origin band transition of $^{13}$C$_6$H is presented. The spectrum is recorded using cavity ring-down spectroscopy in combination with supersonic plasma jets by discharging a $^{13}$C$_2$H$_2$/He/Ar gas mixture. A detailed analysis of more than a hundred fully-resolved transitions allows for an accurate determination of the spectroscopic parameters for both the ground and electronically excited state of $^{13}$C$_6$H.

physics.atom-ph↗
arXiv2014

Laboratory formation of fullerenes from PAHs: Top-down interstellar chemistry

Interstellar molecules are thought to build up in the shielded environment of molecular clouds or in the envelope of evolved stars. This follows many sequential reaction steps of atoms and simple molecules in the gas phase and/or on (icy) grain surfaces. However, these chemical routes are highly inefficient for larger species in the tenuous environment of space as many steps are involved and, indeed, models fail to explain the observed high abundances. This is definitely the case for the C$_{60}$ fullerene, recently identified as one of the most complex molecules in the interstellar medium. Observations have shown that, in some PDRs, its abundance increases close to strong UV-sources. In this letter we report laboratory findings in which C$_{60}$ formation can be explained by characterizing the photochemical evolution of large PAHs. Sequential H losses lead to fully dehydrogenated PAHs and subsequent losses of C$_{2}$ units convert graphene into cages. Our results present for the first time experimental evidence that PAHs in excess of 60 C-atoms efficiently photo-isomerize to Buckminsterfullerene, C$_{60}$. These laboratory studies also attest to the importance of top-down synthesis routes for chemical complexity in space.

astro-ph.IM↗
arXiv2014

On the relevance of the H2 + O reaction pathway for the surface formation of interstellar water - A combined experimental and modeling study

The formation of interstellar water has been commonly accepted to occur on the surfaces of icy dust grains in dark molecular clouds at low temperatures (10-20 K), involving hydrogenation reactions of oxygen allotropes. As a result of the large abundances of molecular hydrogen and atomic oxygen in these regions, the reaction H2 + O has been proposed to contribute significantly to the formation of water as well. However, gas phase experiments and calculations, as well as solid-phase experimental work contradict this hypothesis. Here, we use precisely executed temperature programmed desorption (TPD) experiments in an ultra-high vacuum setup combined with kinetic Monte Carlo simulations to establish an upper limit of the water production starting from H2 and O. These reactants are brought together in a matrix of CO2 in a series of (control) experiments at different temperatures and with different isotopological compositions. The amount of water detected with the quadrupole mass spectrometer upon TPD is found to originate mainly from contamination in the chamber itself. However, if water is produced in small quantities on the surface through H2 + O, this can only be explained by a combined classical and tunneled reaction mechanism. An absolutely conservative upper limit for the reaction rate is derived with a microscopic kinetic Monte Carlo model that converts the upper limit into a maximal possible reaction rate. Incorporating this rate into simulations run for astrochemically relevant parameters, shows that the upper limit to the contribution of the reaction H2 + O in OH, and hence water formation, is 11% in dense interstellar clouds. Our combined experimental and theoretical results indicate however, that this contribution is likely to be much lower.

astro-ph.GA↗
arXiv2013

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.

astro-ph.GA↗
arXiv2013

Wavelength-dependent UV photodesorption of pure N2 and O2 ices

Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Tunable radiation from the DESIRS beamline at the SOLEIL synchrotron in the astrophysically relevant 7 to 13.6 eV range is used to irradiate pure N2 and O2 thin ice films. Photodesorption of molecules is monitored through quadrupole mass spectrometry. Absolute rates are calculated by using the well-calibrated CO photodesorption rates. Strategic N2 and O2 isotopolog mixtures are used to investigate the importance of dissociation upon irradiation. N2 photodesorption mainly occurs through excitation of the b^1Pi_u state and subsequent desorption of surface molecules. The observed vibronic structure in the N2 photodesorption spectrum, together with the absence of N3 formation, supports that the photodesorption mechanism of N2 is similar to CO, i.e., an indirect DIET (Desorption Induced by Electronic Transition) process without dissociation of the desorbing molecule. In contrast, O2 photodesorption in the 7 - 13.6 eV range occurs through dissociation and presents no vibrational structure. Photodesorption rates of N2 and O2 integrated over the far-UV field from various star-forming environments are lower than for CO. Rates vary between 10E-3 and 10E-2 photodesorbed molecules per incoming photon.

astro-ph.GA↗
arXiv2013

Anomalous CO2 Ice Toward HOPS-68: A Tracer of Protostellar Feedback

We report the detection of a unique CO2 ice band toward the deeply embedded, low-mass protostar HOPS-68. Our spectrum, obtained with the Infrared Spectrograph onboard the Spitzer Space Telescope, reveals a 15.2 micron CO2 ice bending mode profile that cannot modeled with the same ice structure typically found toward other protostars. We develop a modified CO2 ice profile decomposition, including the addition of new high-quality laboratory spectra of pure, crystalline CO2 ice. Using this model, we find that 87-92% of the CO2 is sequestered as spherical, CO2-rich mantles, while typical interstellar ices show evidence of irregularly-shaped, hydrogen-rich mantles. We propose that (1) the nearly complete absence of unprocessed ices along the line-of-sight is due to the flattened envelope structure of HOPS-68, which lacks cold absorbing material in its outer envelope, and possesses an extreme concentration of material within its inner (10 AU) envelope region and (2) an energetic event led to the evaporation of inner envelope ices, followed by cooling and re-condensation, explaining the sequestration of spherical, CO2 ice mantles in a hydrogen-poor mixture. The mechanism responsible for the sublimation could be either a transient accretion event or shocks in the interaction region between the protostellar outflow and envelope. The proposed scenario is consistent with the rarity of the observed CO2 ice profile, the formation of nearly pure CO2 ice, and the production of spherical ice mantles. HOPS-68 may therefore provide a unique window into the protostellar feedback process, as outflows and heating shape the physical and chemical structure of protostellar envelopes and molecular clouds.

astro-ph.SR↗
arXiv2011

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.

astro-ph.GA↗