Wolf D. Geppert

A KINETIC DATABASE FOR ASTROCHEMISTRY (KIDA)

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of zero-dimensional and one-dimensional interstellar sources.

Reaction networks for interstellar chemical modelling: Improvements and challenges.

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes—ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination—is reviewed. Emphasis is placed on those key reactions that have been identified, by sensitivity analyses, as ‘crucial’ in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalyzed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.

Ion chemistry in space

We review the gas-phase chemistry in extraterrestrial space that is driven by reactions with atomic and molecular ions. Ions are ubiquitous in space and are potentially responsible for the formation of increasingly complex interstellar molecules. Until recently, positively charged atoms and molecules were the only ions known in space; however, this situation has changed with the discovery of various molecular anions. This review covers not only the observation, distribution and reactions of ions in space, but also laboratory-based experimental and theoretical methods for studying these ions. Recent results from space-based instruments, such as those on the Cassini-Huygens space mission and the Herschel Space Observatory, are highlighted.

The 2014 KIDA network for interstellar chemistry

Chemical models used to study the chemical composition of the gas and the ices in the interstellar medium are based on a network of chemical reactions and associated rate coefficients. These reacti ...

Dissociative Recombination of N2H+: Evidence for Fracture of the N-N Bond

Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2H+ using the CRYRING ion storage ring. It has been found that the channel N2H+ + e- → N2 + H accounts for only 36% of the total reaction and that the branching into the other exoergic pathway, N2H+ + e- → NH + N, consequently amounts to 64%. The cross section of the reaction could be fitted by the expression σ = (2.4 ± 0.4) × 10-16E-1.04±0.02 cm2, which leads to a thermal reaction rate of k(T) = (1.0 ± 0.2) × 10-7(T/300)-0.51±0.02 cm3 s-1, in favorable agreement with previous flowing afterglow Langmuir probe measurements at room temperature, although our temperature dependence is very different. The implications of these measurements for the chemistry of interstellar clouds are discussed. A standard model calculation for a dark cloud predicts a slight increase of N2H+ in the dark clouds but a five- to sevenfold increase of the NH concentration as steady state is reached.

A spectral line survey of Orion KL in the bands 486-492 and 541-577 GHz with the Odin satellite - II. Data analysis

Aims. We investigate the physical and chemical conditions in a typical star forming region, including an unbiased search for new molecules in a spectral region previously unobserved. Methods. Due to its proximity, the Orion KL region offers a unique laboratory of molecular astrophysics in a chemically rich, massive star forming region. Several ground-based spectral line surveys have been made, but due to the absorption by water and oxygen, the terrestrial atmosphere is completely opaque at frequencies around 487 and 557 GHz. To cover these frequencies we used the Odin satellite to perform a spectral line survey in the frequency ranges 486−492 GHz and 541−577 GHz, filling the gaps between previous spectral scans. Odin’s high main beam efficiency, ηmb = 0.9, and observations performed outside the atmosphere make our intensity scale very well determined. Results. We observed 280 spectral lines from 38 molecules including isotopologues, and, in addition, 64 unidentified lines. A few U-lines have interesting frequency coincidences such as ND and the anion SH − . The beam-averaged emission is dominated by CO, H2O, SO2 ,S O, 13 CO and CH3OH. Species with the largest number of lines are CH3OH, (CH3)2O, SO2, 13 CH3OH, CH3CN and NO. Six water lines are detected including the ground state rotational transition 11,0–10,1 of o-H2O, its isotopologues o-H 18 Oa nd o-H 17 O, the Hot Core tracing p-H2O transition 62,4–71,7 ,a nd the 2 0,2–11,1 transition of HDO. Other lines of special interest are the 10–0 0 transition of NH3 and its isotopologue 15 NH3. Isotopologue abundance ratios of D/H, 12 C/ 13 C, 32 S/ 34 S, 34 S/ 33 S, and 18 O/ 17 O are estimated. The temperatures, column densities and abundances in the various subregions are estimated, and we find very high gas-phase abundances of H2O, NH3 ,S O 2, SO, NO, and CH3OH. A comparison with the ice inventory of ISO sheds new light on the origin of the abundant gas-phase molecules.

Evidence for a strong intermolecular bond in the phenol⋅N2 cation

The phenol⋅N2 complex cation has been studied with a combination of two-color resonant zero kinetic energy (ZEKE) and mass analyzed threshold ionization (MATI) spectroscopies to probe the interaction of a polar cation with a quadrupolar solvent molecule. Extended vibrational progressions are observed in three modes which are assigned as the in-plane bend (35 cm−1), the stretch (117 cm−1), and in-plane wag (130 cm−1) intermolecular vibrations, and are consistent with a structure where the N2 forms a directional bond to the phenol OH group in the plane of the aromatic ring. Ab initio calculations at the UMP2/6-31G*, UHF/cc-pVDZ, and UMP2/cc-pVDZ levels of theory support this assignment. The spectra also provide a value for the adiabatic ionization energy (67 423 cm−1±4.5 cm−1) and an estimate of the dissociation energy of the cluster (1650±20 cm−1) which illustrate that the quadrupolar nitrogen molecule binds considerably more strongly to the phenol cation than a rare gas atom. These results constitute the ...

Observational tests of interstellar methanol formation

Context. It has been established that the classical gas-phase production of interstellar methanol (CH3OH) cannot explain observed abundances. Instead it is now generally thought that the main formation path has to be by successive hydrogenation of solid CO on interstellar grain surfaces. Aims. While theoretical models and laboratory experiments show that methanol is efficiently formed from CO on cold grains, our aim is to test this scenario by astronomical observations of gas associated with young stellar objects (YSOs). Methods. We have observed the rotational transition quartets J = 2K –1 K of 12 CH3OH and 13 CH3OH at 96.7 and 94.4 GHz, respectively, towards a sample of massive YSOs in different stages of evolution. In addition, the J = 1−0 transitions of 12 C 18 Oa nd 13 C 18 O were observed towards some of these sources. We use the 12 C/ 13 C ratio to discriminate between gas-phase and grain surface origin: If methanol is formed from CO on grains, the ratios should be similar in CH3OH and CO. If not, the ratio should be higher in CH3OH due to 13 C fractionation in cold CO gas. We also estimate the abundance ratios between the nuclear spin types of methanol (E and A). If methanol is formed on grains, this ratio is likely to have been thermalized at the low physical temperature of the grain, and therefore show a relative over-abundance of A-methanol. Results. We show that the 12 C/ 13 C isotopic ratio is very similar in gas-phase CH3OH and C 18 O, on the spatial scale of about 40 �� , towards four YSOs. For two of our sources we find an overabundance of A-methanol as compared to E-methanol, corresponding to nuclear spin temperatures of 10 and 16 K. For the remaining five sources, the methanol E/A ratio is less than unity. Conclusions. While the 12 C/ 13 C ratio test is consistent with methanol formation from hydrogenation of CO on grain surfaces, the result of the E/A ratio test is inconclusive.

First storage of ion beams in the Double Electrostatic Ion-Ring Experiment: DESIREE

We report on the first storage of ion beams in the Double ElectroStatic Ion Ring ExpEriment, DESIREE, at Stockholm University. We have produced beams of atomic carbon anions and small carbon anion molecules (C(n)(-), n = 1, 2, 3, 4) in a sputter ion source. The ion beams were accelerated to 10 keV kinetic energy and stored in an electrostatic ion storage ring enclosed in a vacuum chamber at 13 K. For 10 keV C2 (-) molecular anions we measure the residual-gas limited beam storage lifetime to be 448 s ± 18 s with two independent detector systems. Using the measured storage lifetimes we estimate that the residual gas pressure is in the 10(-14) mbar range. When high current ion beams are injected, the number of stored particles does not follow a single exponential decay law as would be expected for stored particles lost solely due to electron detachment in collision with the residual-gas. Instead, we observe a faster initial decay rate, which we ascribe to the effect of the space charge of the ion beam on the storage capacity.

Dissociative recombination of highly enriched para-H-3(+)

The determination of the dissociative recombination rate coefficient of H(3) (+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H(3) (+) and para-H(3) (+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H(3) (+) in the diffuse interstellar medium, where H(3) (+) has been widely observed. We present the results of an experiment at the CRYRING ion storage ring in which we investigated the dissociative recombination of highly enriched ( approximately 83.6%) para-H(3) (+) using a supersonic expansion source that produced ions with T(rot) approximately 60-100 K. We observed an increase in the low energy recombination rate coefficient of the enriched para-H(3) (+) by a factor of approximately 1.25 in comparison to H(3) (+) produced from normal H(2) (ortho:para=3:1). The ratio of the rate coefficients of pure para-H(3) (+) to that of pure ortho-H(3) (+) is inferred to be approximately 2 at low collision energies; the corresponding ratio of the thermal rate coefficients is approximately 1.5 at electron temperatures from 60 to 1000 K. We conclude that this difference is unlikely to have an impact on the interstellar ortho:para ratio of H(3) (+).