Importance of the Hydrogen Isocyanide Isomer in Modeling Hydrogen Cyanide Oxidation in Combustion

This article re-examines the chemistry of hydrogen isocyanide (HNC) and its role in combustion nitrogen chemistry

Laboratory Measurement of the Pure Rotational Transitions of the HCNH+ and its Isotopic Species

The pure rotational transitions of the protonated hydrogen cyanide ion, HCNH+, and its isotopic species, HCND+ and DCND+, were measured in the 107 - 482 GHz region with a source modulated microwave spectrometer. The ions were generated in the cell with a magnetically confined dc-glow discharge of HCN and/or DCN. The rotational constant B0 and the centrifugal distortion constant D0 for each ion were precisely determined by a least-squares fitting to the observed spectral lines. The observed rotational transition frequencies by laboratory spectroscopy and the predicted ones are accurate in about 30 to 40 kHz and are useful as rest frequencies for astronomical searches of HCNH+ and HCND+.Comment: 14 pages in TeX, 1 figures in JPE

The IRAM-30m line survey of the Horsehead PDR: II. First detection of the l-C3H+ hydrocarbon cation

We present the first detection of the l-C3H+ hydrocarbon in the interstellar medium. The Horsehead WHISPER project, a millimeter unbiased line survey at two positions, namely the photo-dissociation region (PDR) and the nearby shielded core, revealed a consistent set of eight unidentified lines toward the PDR position. Six of them are detected with a signal-to-noise ratio from 6 to 19, while the two last ones are tentatively detected. Mostly noise appears at the same frequency toward the dense core, located less than 40" away. We simultaneously fit 1) the rotational and centrifugal distortion constants of a linear rotor, and 2) the Gaussian line shapes located at the eight predicted frequencies. The observed lines can be accurately fitted with a linear rotor model, implying a 1Sigma ground electronic state. The deduced rotational constant value is Be= 11244.9512 +/- 0.0015 MHz, close to that of l-C3H. We thus associate the lines to the l-C3H+ hydrocarbon cation, which enables us to constrain the chemistry of small hydrocarbons. A rotational diagram is then used to infer the excitation temperature and the column density. We finally compare the abundance to the results of the Meudon PDR photochemical model.Comment: 9 pages, 7 PostScript figures. Accepted for publication in Astronomy \& Astrophysics. Uses aa LaTeX macro

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 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-catalysed 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.Comment: Accepted for publication in Space Science Review

Pressure Dependent Low Temperature Kinetics for CN + CH3CN: Competition between Chemical Reaction and van der Waals Complex Formation

International audienceThe gas phase reaction between the CN radical and acetonitrile CH3CN was investigated experimentally, at low temperatures, with the CRESU apparatus and a slow flow reactor to explore the temperature dependence of its rate coefficient from 354 K down to 23 K. Whereas a standard Arrhenius behavior was found at T > 200 K, indicating the presence of an activation barrier, a dramatic increase in the rate coefficient by a factor of 130 was observed when the temperature was decreased from 168 to 123 K. The reaction was found to be pressure independent at 297 K unlike the experiments carried out at 52 and 132 K. The work was complemented by ab initio transition state theory based master equation calculations using reaction pathways investigated with highly accurate thermochemical protocols. The role of collisional stabilization of a CN⋯CH3CN van der Waals complex and of tunneling induced H atom abstractions were also considered. The experimental pressure dependence at 52 and 132 K is well reproduced by the theoretical calculations provided that an anharmonic state density is considered for the van der Waals complex CH3CN⋯CN and its Lennard-Jones radius is adjusted. Furthermore, these calculations indicate that the experimental observations correspond to the fall-off regime and that tunneling remains small in the low-pressure regime. Hence, the studied reaction is essentially an association process at very low temperature. Implications for the chemistry of interstellar clouds and Titan are discussed

An Agent-Based Approach to Self-Organized Production

The chapter describes the modeling of a material handling system with the production of individual units in a scheduled order. The units represent the agents in the model and are transported in the system which is abstracted as a directed graph. Since the hindrances of units on their path to the destination can lead to inefficiencies in the production, the blockages of units are to be reduced. Therefore, the units operate in the system by means of local interactions in the conveying elements and indirect interactions based on a measure of possible hindrances. If most of the units behave cooperatively ("socially"), the blockings in the system are reduced. A simulation based on the model shows the collective behavior of the units in the system. The transport processes in the simulation can be compared with the processes in a real plant, which gives conclusions about the consequencies for the production based on the superordinate planning.Comment: For related work see http://www.soms.ethz.c

Spatially Resolved Chemistry in Nearby Galaxies I. The Center of IC 342

We have imaged emission from the millimeter lines of eight molecules--C2H, C34S, N2H+, CH3OH, HNCO, HNC, HC3N, and SO--in the central half kpc of the nearby spiral galaxy IC 342. The 5" (~50 pc) resolution images were made with OVRO. Using these maps we obtain a picture of the chemistry within the nuclear region on the sizescales of individual GMCs. Bright emission is detected from all but SO. There are marked differences in morphology for the different molecules. A principal component analysis is performed to quantify similarities and differences among the images. This analysis reveals that while all molecules are to zeroth order correlated, that is, they are all found in dense molecular clouds, there are three distinct groups of molecules distinguished by the location of their emission within the nuclear region. N2H+, C18O, HNC and HCN are widespread and bright, good overall tracers of dense molecular gas. C2H and C34S, tracers of PDR chemistry, originate exclusively from the central 50-100 pc region, where radiation fields are high. The third group of molecules, CH3OH and HNCO, correlates well with the expected locations of bar-induced orbital shocks. The good correlation of HNCO with the established shock tracer molecule CH3OH is evidence that this molecule, whose chemistry has been uncertain, is indeed produced by processing of grains. HC3N is observed to correlate tightly with 3mm continuum emission, demonstrating that the young starbursts are the sites of the warmest and densest molecular gas. We compare our HNC images with the HCN images of Downes et al. (1992) to produce the first high resolution, extragalactic HCN/HNC map: the HNC/HCN ratio is near unity across the nucleus and the correlation of both of these gas tracers with the star formation is excellent. (Abridged).Comment: 54 pages including 10 figures and 8 tables. Accepted for publication in Ap

First-principles extrapolation method for accurate CO adsorption energies on metal surfaces

We show that a simple first-principles correction based on the difference between the singlet-triplet CO excitation energy values obtained by DFT and high-level quantum chemistry methods yields accurate CO adsorption properties on a variety of metal surfaces. We demonstrate a linear relationship between the CO adsorption energy and the CO singlet-triplet splitting, similar to the linear dependence of CO adsorption energy on the energy of the CO 2$\pi$* orbital found recently {[Kresse {\em et al.}, Physical Review B {\bf 68}, 073401 (2003)]}. Converged DFT calculations underestimate the CO singlet-triplet excitation energy $\Delta E_{\rm S-T}$, whereas coupled-cluster and CI calculations reproduce the experimental $\Delta E_{\rm S-T}$. The dependence of $E_{\rm chem}$ on $\Delta E_{\rm S-T}$ is used to extrapolate $E_{\rm chem}$ for the top, bridge and hollow sites for the (100) and (111) surfaces of Pt, Rh, Pd and Cu to the values that correspond to the coupled-cluster and CI $\Delta E_{\rm S-T}$ value. The correction reproduces experimental adsorption site preference for all cases and obtains $E_{\rm chem}$ in excellent agreement with experimental results.Comment: Table sent as table1.eps. 3 figure

A Stable and Robust Calibration Scheme of the Log-Periodic Power Law Model

We present a simple transformation of the formulation of the log-periodic power law formula of the Johansen-Ledoit-Sornette model of financial bubbles that reduces it to a function of only three nonlinear parameters. The transformation significantly decreases the complexity of the fitting procedure and improves its stability tremendously because the modified cost function is now characterized by good smooth properties with in general a single minimum in the case where the model is appropriate to the empirical data. We complement the approach with an additional subordination procedure that slaves two of the nonlinear parameters to what can be considered to be the most crucial nonlinear parameter, the critical time $t_c$ defined as the end of the bubble and the most probably time for a crash to occur. This further decreases the complexity of the search and provides an intuitive representation of the results of the calibration. With our proposed methodology, metaheuristic searches are not longer necessary and one can resort solely to rigorous controlled local search algorithms, leading to dramatic increase in efficiency. Empirical tests on the Shanghai Composite index (SSE) from January 2007 to March 2008 illustrate our findings

Molecular fluorine chemistry in the early Universe

Some models of Big Bang nucleosynthesis suggest that very high baryon density regions were formed in the early Universe, and generated the production of heavy elements other than lithium such as fluorine F. We present a comprehensive chemistry of fluorine in the post-recombination epoch. Calculation of F, F- and HF abundances, as a function of redshift z, are carried out. The main result is that the chemical conditions in the early Universe can lead to the formation of HF. The final abundance of the diatomic molecule HF is predicted to be close to 3.75 10(-17) when the initial abundance of neutral fluorine F is 10(-15). These results indicate that molecules of fluorine HF were already present during the dark age. This could have implications on the evolution of proto-objects and on the anisotropies of cosmic microwave background radiation. Hydride of fluorine HF may affect enhancement of the emission line intensity from the proto-objects and could produce spectral-spatial fluctuations.Comment: Accepted in Astronomy and Astrophysics, 7 pages, 2 figure