Jordy Bouwman

THE c2d SPITZER SPECTROSCOPIC SURVEY OF ICES AROUND LOW-MASS YOUNG STELLAR OBJECTS. IV. NH3 AND CH3OH

NH_3 and CH_3OH are key molecules in astrochemical networks leading to the formation of more complex N- and O-bearing molecules, such as CH3CN and CH3OCH3. Despite a number of recent studies, little is known about their abundances in the solid state. This is particularly the case for low-mass protostars, for which only the launch of the Spitzer Space Telescope has permitted high-sensitivity observations of the ices around these objects. In this work, we investigate the ~8–10μm region in the Spitzer IRS (InfraRed Spectrograph) spectra of 41 low-mass young stellar objects (YSOs). These data are part of a survey of interstellar ices in a sample of low-mass YSOs studied in earlier papers in this series. We used both an empirical and a local continuum method to correct for the contribution from the 10μm silicate absorption in the recorded spectra. In addition, we conducted a systematic laboratory study of NH_(3-) and CH_3OH-containing ices to help interpret the astronomical spectra. We clearly detect a feature at ~9μm in 24 low-mass YSOs. Within the uncertainty in continuum determination, we identify this feature with the NH_3 ν_2 umbrella mode and derive abundances with respect to water between ~2% and 15%. Simultaneously, we also revisited the case of CH_3OH ice by studying the ν_4 C–O stretch mode of this molecule at ~9.7μm in 16 objects, yielding abundances consistent with those derived by Boogert et al. based on a simultaneous 9.75 and 3.53μm data analysis. Our study indicates that NH_3 is present primarily in H_2O-rich ices, but that in some cases, such ices are insufficient to explain the observed narrow FWHM. The laboratory data point to CH_3OH being in an almost pure methanol ice, or mixed mainly with CO or CO_2, consistent with its formation through hydrogenation on grains. Finally, we use our derived NH_3 abundances in combination with previously published abundances of other solid N-bearing species to find that up to 10%–20% of nitrogen is locked up in known ices.

CAN NEUTRAL AND IONIZED POLYCYCLIC AROMATIC HYDROCARBONS BE CARRIERS OF THE ULTRAVIOLET EXTINCTION BUMP AND THE DIFFUSE INTERSTELLAR BANDS

Up to now, no laboratory-based study has investigated polycyclic aromatic hydrocarbon (PAH) species as potential carriers of both the diffuse interstellar bands (DIBs) and the 2175 A UV bump. We examined the proposed correlation between these two features by applying experimental and theoretical techniques on two specific medium-sized/large PAHs (dibenzorubicene C30H14 and hexabenzocoronene C42H18) in their neutral and cationic states. It was already shown that mixtures of sufficiently large, neutral PAHs can partly or even completely account for the UV bump. We investigated how the absorption bands are altered upon ionization of these molecules by interstellar UV photons. The experimental studies presented here were realized by performing matrix isolation spectroscopy with subsequent far-UV irradiation. The main effects were found to be a broadening of the absorption bands in the UV combined with slight red shifts. The position of the complete pi - pi* absorption structure around 217.5 nm, however, remains more or less unchanged which could explain the observed position invariance of the interstellar bump for different lines of sight. This favors the assignment of this feature to the interstellar PAH population. As far as the DIBs are concerned, neither our investigations nor the laboratory studies carried out by other research groups support a possible connection with this class of molecules. Instead, there are reasonable arguments that neutral and singly ionized cationic PAHs cannot be made responsible for the DIBs.

REAL-TIME OPTICAL SPECTROSCOPY OF VACUUM ULTRAVIOLET IRRADIATED PYRENE:H2O INTERSTELLAR ICE

This paper describes a near-UV/VIS study of a pyrene:H2O interstellar ice analogue at 10 K using optical absorption spectroscopy. A new experimental approach makes it possible to irradiate the sample with vacuum ultraviolet (VUV) light (7-10.5 eV) while simultaneously recording spectra in the 240-1000 nm range with subsecond time resolution. Both spectroscopic and dynamic information on VUV processed ices are obtained in this way. This provides a powerful tool to follow, in situ and in real time, the photophysical and photochemical processes induced by VUV irradiation of a polycyclic aromatic hydrocarbon containing inter- and circumstellar ice analogue. Results on the VUV photolysis of a prototype sample—strongly diluted pyrene in H2O ice—are presented. In addition to the pyrene cation (Py+), other products—hydroxypyrene (PyOH), possibly hydroxypyrene cation (PyOH+), and pyrene/pyrenolate anion (Py–/PyO–)—are observed. It is found that the charge remains localized in the ice, also after the VUV irradiation is stopped. The astrochemical implications and observational constraints are discussed.

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice I. Mid-IR spectroscopy and photoproducts

Context. Polycyclic aromatic hydrocarbons (PAHs) are known to be abundantly present in photon-dominated regions (PDRs), as evidenced by their ubiquitous mid-IR emission bands. Towards dense clouds, however, their IR emission bands are strongly suppressed. It is here where molecules are known to reside on very cold grains (T ≤ 30 K) in the form of interstellar ices. Therefore, it is likely that non-volatile species, such as PAHs, also freeze out on grains. Such icy grains act as catalytic sites and, upon vacuum ultraviolet (VUV) irradiation, chemical reactions are initiated. In the study presented here, these reactions and the resulting photoproducts are investigated for PAH containing water ices. Aims. The aim of this work is to monitor vacuum ultraviolet induced chemical reactions of PAHs in cosmic ice through their IR signatures, to characterize the families of species formed in these reactions, and to apply the results to astronomical observations. Methods. Mid-infrared Fourier transform absorption spectroscopic measurements ranging from 6500 to 450 cm −1 are performed on freshly deposited and vacuum ultraviolet processed PAH containing cosmic H2O ices at low temperatures. Results. The mid-IR spectroscopy of anthracene, pyrene and benzo[ghi]perylene containing H2O ice is reported. Band strengths of the neutral PAH modes in H2O ice are derived. Additionally, spectra of vacuum ultraviolet processed PAH containing H2O ices are presented. These spectra are compared to spectra measured in VUV processed PAH:argon matrix isolation studies. It is concluded that the parent PAH species is ionized in H2O ice and that other photoproducts, mainly more complex PAH derivatives, also form. The importance of PAHs and their PAH:H2O photoproducts in astronomical mid-infrared spectroscopic studies, in particular in the 5−8 μm region, is discussed. As a test-case, the VUV photolyzed PAH:H2O laboratory spectra are compared to a high resolution ISOSWS spectrum of the high-mass embedded protostar W33A and to a Spitzer spectrum of the low-mass Young Stellar Object (YSO) RNO 91. For these objects, an upper limit of 2–3% with respect to H2O ice is derived for the contribution of PAHs and PAH:H2O photoproducts to the absorbance in the 5−8 μm region towards these objects.

Photochemistry of the PAH pyrene in water ice: the case for ion-mediated solid-state astrochemistry

Context. Icy dust grains play an important role in the formation of complex molecules in the interstellar medium (ISH). Laboratory studies have mainly focused on the physical interactions and chemical pathways in ices containing rather simple molecules, such as H2O, CO, CO2 ,C H 4 ,a nd CH 3OH. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are also abundantly present in the ISM in the gas phase. It is likely that these non-volatile species also freeze-out onto dust grains and participate in the astrochemical solid-state network, but additional experimental PAH ice studies are largely lacking. Aims. The study presented here focuses on a rather small PAH, pyrene (C16H10), and aims to understand and quantify photochemical reactions of PAHs in interstellar ices upon vacuum ultraviolet (VUV) irradiation as a function of astronomically relevant parameters. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, H2O and CO. Pyrene ionization is found to be most efficient in H2O ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py ·+ ,a nd PyH · are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionized in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are placed in an astrophysical context by determining the importance of PAH ionization in a molecular cloud. We conclude that the rate of pyrene ionization in water ice mantles is comparable to the rate of photodesorption of H2O ice. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.

Photochemistry of polycyclic aromatic hydrocarbons in cosmic water ice - II. Near UV/VIS spectroscopy and ionization rates

Context. Mid-infrared emission features originating from polycyclic aromatic hydrocarbons (PAHs) are observed towards photon dominated regions in space. Towards dense clouds, however, these emission features are quenched. Observations of dense clouds show that many simple volatile molecules are frozen out on interstellar grains, forming thin layers of ice. Recently, observations have shown that more complex non-volatile species, presumably including PAHs, also freeze out and contribute to the ongoing solid-state chemistry. Aims. The study presented here aims at obtaining reaction rate data that characterize PAH photochemistry upon vacuum ultraviolet (VUV) irradiation in an interstellar H2O ice analogue to explore the potential impact of PAH:H2O ice reactions on overall interstellar ice chemistry. To this end, the experimental results are implemented in a chemical model under simple interstellar cloud conditions. Methods. Time-dependent near-UV/VIS spectroscopy on the VUV photochemistry of anthracene, pyrene, benzo[ghi]perylene and coronene containing interstellar H2O ice analogs is performed at 25 and 125 K, using an optical absorption setup. Results. Near-UV/VIS absorption spectra are presented for these four PAHs and their photoproducts including cationic species trapped in H 2O ice. Oscillator strengths of the cation absorption bands are derived relative to the oscillator strength of the neutral parent PAH. The loss of the parent and growth of PAH photoproducts are measured as a function of VUV dose, yielding solid state reaction constants. The rate constants are used in an exploratory astrochemical model, to assess the importance of PAH:H2 Oi ce photoprocessing in UV exposed interstellar environments, compared with the timescales in which PAH molecules are incorporated in interstellar ices. Conclusions. All four PAHs studied here are found to be readily ionized upon VUV photolysis when trapped in H2O ice and exhibit similar rates for ionization at astronomically relevant temperatures. Depending on the relative efficiency of H2O photodesorption and PAH photoionization in H2O ice, the latter may trigger a charge induced aromatic solid state chemistry, in which PAH cations play a central role.

Dissociative photoionization of quinoline and isoquinoline

Two nitrogen-containing polycyclic aromatic hydrocarbon isomers of C9H7N composition, quinoline, and isoquinoline have been studied by imaging photoelectron photoion coincidence spectroscopy at the VUV beamline of the Swiss Light Source. High resolution threshold photoelectron spectra have been recorded and are interpreted applying a Franck-Condon model. Dissociative ionization mass spectra as a function of the parent ion internal energy are analyzed with the use of breakdown diagrams. HCN loss and H loss are the dominant dissociation paths for both C9H7N(•+) isomers at photon energies below 15.5 eV. Computed C9H7N(•+) potential energy surfaces suggest that the lowest energy path leading to HCN-loss yields the benzocyclobutadiene cation. A statistical model is used to fit the breakdown diagram and-to account for the kinetic shift-the time-of-flight mass spectra that reveal the dissociation rates. We have derived appearance energies of 11.9 ± 0.1 (HCN loss) and 12.0 ± 0.1 (H loss), as well as 11.6 ± 0.2 (HCN loss) and 12.1 ± 0.2 (H loss) eV, for the dissociative ionization of quinoline and isoquinoline, respectively. The results are compared to a recent study on the dissociative ionization of naphthalene. Implications for the formation and destruction of nitrogenated PAHs in the interstellar medium and in Titans atmosphere are highlighted.

Band profiles and band strengths in mixed H2O:CO ices

Context. Laboratory spectroscopic research plays a key role in the identification and analysis of interstellar ices and their structure. To date, a number of molecules have been positively identified in interstellar ices, either as pure, mixed or layered ice structures. Aims. Previous laboratory studies on H2O:CO ices have employed a “mix and match” principle and describe qualitatively how absorption bands behave for different physical conditions. The aim of this study is to quantitatively characterize the absorption bands of solid CO and H2O, both pure and in their binary mixtures, as a function of partner concentration and temperature. Methods. Laboratory measurements based on Fourier transform infrared transmission spectroscopy are performed on binary mixtures of H2O and CO ranging from 1:4 to 4:1. Results. A quantitative analysis of the band profiles and band strengths of H2O in CO ice, and vice versa, is presented and interpreted in terms of two models. The results show that a mutual interaction takes place between the two species in the solid, which alters the band positions and band strengths. It is found that the band strengths of the H2O bulk stretch, bending and libration vibrational bands decrease linearly by a factor of up to 2 when the CO concentration is increased from 0 to 80%. By contrast, the band strength of the free OH stretch increases linearly. The results are compared to a recently performed quantitative study on H2O:CO2 ice mixtures. It is shown that for mixing ratios of 1:0.5 H2O:X and higher, the H2O bending mode offers a good tracer to distinguish between CO2 or CO in H2O ice. Additionally, it is found that the band strength of the CO fundamental remains constant when the water concentration is increased in the ice. The integrated absorbance of the 2152 cm −1 CO feature, with respect to the total integrated CO absorption feature, is found to be a good indicator of the degree of mixing of CO in the H2O:CO laboratory ice system. From the change in the H2O absorption band strength in laboratory ices upon mixing we conclude that astronomical water ice column densities on various lines of sight can be underestimated by up to 25% if significant amounts of CO and CO2 are mixed in.

Bimolecular Rate Constant and Product Branching Ratio Measurements for the Reaction of C2H with Ethene and Propene at 79 K

The reactions of the ethynyl radical (C(2)H) with ethene (C(2)H(4)) and propene (C(3)H(6)) are studied under low temperature conditions (79 K) in a pulsed Laval nozzle apparatus. Ethynyl radicals are formed by 193 nm photolysis of acetylene (C(2)H(2)) and the reactions are studied in nitrogen as a carrier gas. Reaction products are sampled and subsequently photoionized by the tunable vacuum ultraviolet radiation of the Advanced Light Source (ALS) at Lawrence Berkeley National Laboratory. The product ions are detected mass selectively and time-resolved by a quadrupole mass spectrometer. Bimolecular rate coefficients are determined under pseudo-first-order conditions, yielding values in good agreement with previous measurements. Photoionization spectra are measured by scanning the ALS photon energy while detecting the ionized reaction products. Analysis of the photoionization spectra yields-for the first time-low temperature isomer resolved product branching ratios. The reaction between C(2)H and ethene is found to proceed by H-loss and yields 100% vinylacetylene. The reaction between C(2)H and propene results in (85 ± 10)% C(4)H(4) (m/z = 52) via CH(3)-loss and (15 ± 10)% C(5)H(6) (m/z = 66) by H-loss. The C(4)H(4) channel is found to consist of 100% vinylacetylene. For the C(5)H(6) channel, analysis of the photoionization spectrum reveals that (62 ± 16)% is in the form of 4-penten-1-yne, (27 ± 8)% is in the form of cis- and trans-3-penten-1-yne and (11 ± 10)% is in the form of 2-methyl-1-buten-3-yne.

Product detection of the CH radical reaction with acetaldehyde

The reaction of the methylidyne radical (CH) with acetaldehyde (CH(3)CHO) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of CHBr(3) and react with acetaldehyde in an excess of helium and nitrogen gas flow. Five reaction exit channels are observed corresponding to elimination of methylene (CH(2)), elimination of a formyl radical (HCO), elimination of carbon monoxide (CO), elimination of a methyl radical (CH(3)), and elimination of a hydrogen atom. Analysis of the photoionization yields versus photon energy for the reaction of CH and CD radicals with acetaldehyde and CH radical with partially deuterated acetaldehyde (CD(3)CHO) provides fine details about the reaction mechanism. The CH(2) elimination channel is found to preferentially form the acetyl radical by removal of the aldehydic hydrogen. The insertion of the CH radical into a C-H bond of the methyl group of acetaldehyde is likely to lead to a C(3)H(5)O reaction intermediate that can isomerize by β-hydrogen transfer of the aldehydic hydrogen atom and dissociate to form acrolein + H or ketene + CH(3), which are observed directly. Cycloaddition of the radical onto the carbonyl group is likely to lead to the formation of the observed products, methylketene, methyleneoxirane, and acrolein.