Calculated Rate Coefficients Research Articles

Rotational excitation of methyl mercaptan (CH3SH) in collisions with molecular hydrogen

Abstract This paper presents the calculation of rate coefficients for transitions between rotational levels of the A-type and E-type levels of methyl mercaptan (CH3SH) resulting from collisions with molecular hydrogen. Radiative transfer modeling requires both radiative and collisional rates to describe the rotational populations under the usual conditions in interstellar clouds where LTE conditions do not apply. To compute the intermolecular interaction between CH3SH and H2, the explicitly correlated CCSD(T)-F12a coupled-cluster method which utilized a correlation-consistent aug-cc-pVTZ basis was employed. The computed energies were fit to a functional form suitable for use in scattering calculations. Rate coefficients were calculated over the temperature range from 5 to 100 K for transitions between the 110 lowest CH3SH rotational levels (having energies less than 107 cm−1 (ca. 150 K) within both the A-type and E-type manifolds caused by collisions with para- and ortho-H2. The rate coefficients were obtained through time-independent quantum close coupling quantum scattering calculations utilizing the calculated PES.

Formation of S2 species in different redox states by radiative association in atomic and ionic collisions

Radiative associations for formations of the S2, S2+ and S2- molecular species during atomic collisions S(3Pu) + S(3Pu), S(3Pu) + S+(4Su) and S(3Pu) + S-(2Pu) are investigated. The adiabatic potential energy curves (PECs) and spin-allowed transition dipole moments (TDMs) are obtained by the internally contracted multireference configuration interaction method with the Davidson correction (icMRCI+Q). A number of PECs and TDMs are chosen to calculate the corresponding cross-sections and rate coefficients of radiative associations. The calculated rate coefficients are valid for the temperatures from 100 to 16000 K and fitted to the analytical function according to the three-parameter Arrhenius–Kooij formula. These results indicate that transitions originating in the ΔΛ=0 selection rule are the main contributors for the radiative association process. The present study can elucidate the further understanding the radiative association, which plays an important role in the formation and evolution of the S2, S2+ and S2- molecules.

Theoretical and experimental study on the pyrolysis of N-methylpyrrolidone

As a widely used organic solvent, N-methylpyrrolidone (NMP) may suffer thermal decomposition during large-scale industrial usage. The complex potential energy surface and corresponding pressure-dependent rate coefficients of NMP and NMP radicals were obtained at a high level of theory. The intermediates and products of NMP pyrolysis within 900–1200 K were identified and measured by synchrotron vacuum ultraviolet photoionization mass spectrometry. Theoretical calculations show that the Keto-enol tautomerization and direct ring-opening channel yielding C2H4, CO, and CH3NCH2 exhibit the highest rate coefficient among NMP unimolecular reactions at low and high temperatures, respectively. However, the fuel decomposition process cannot be exclusively dominated by single low-barrier channel. The ring-opening reaction forming imino aldehyde radical and following decarbonylation reactions are favored channels during the NMP radical decomposition, while the formation of the dihydropyrrolidone via H or CH3 loss competes with them at higher temperatures. Various smaller heterocycle radicals can be produced and act as intermediates for the multi-step isomerization of the ring-opening products with a relatively low energy barrier, changing the position of the functional group and radical site. A variety of nitrogenous and oxygenated species were observed in the experiment, such as ketene, methyl isocyanate, pyrrole, benzene, and different kinds of imines. Among them, C2H4, HCN, and CO are the major products for NMP decomposition. Potential reaction pathways from NMP to the major experimentally observed products were inferred based on the calculated results and existing knowledge on the pyrolysis of nitrogenous and oxygenated compounds. These results shed light on the complex C/H/O/N reaction system. The calculated rate coefficients and extensive mole fractions data could provide good support for the modeling of a detailed reaction mechanism in the future.

Laboratory Benchmark of n ≥ 4 Dielectronic Recombination Satellites of Fe xvii

We calculated cross sections for the dielectronic recombination (DR) satellite lines of Fe xvii and benchmarked our predictions with experimental cross sections of Fe xvii resonances that were monoenergetically excited in an electron-beam ion trap. We extend the benchmark to all resolved DR and direct electron-impact excitation (DE) channels in the experimental data set, specifically the n ≥ 4 DR resonances of Fe xvii, complementing earlier investigations of n = 3 channels. Our predictions for the DR and DE absolute cross sections for the higher n complexes disagree considerably with experimental results when using the same methods as in previous works. However, we achieve agreement within ∼10% of the experimental results by an approach whereby we doubly convolve the predicted cross sections with both the spread of the electron-beam energy and the photon energy resolution of our experiment. We then calculated rate coefficients from the experimental and theoretical cross sections, finding general agreement within 2σ with the rates found in the OPEN-ADAS atomic database.

Forward and reverse uncertainty analyses for RRKM/master equation based kinetic predictions: A case study of ethyl with oxygen

AbstractIn the realm of combustion kinetic modeling, the norm involves employing thousands of reactions to delineate the chemical conversion of hundreds of species. Notably, theoretically predicted rate coefficients and branching ratios, derived through the RRKM/master equation (ME) model, play an increasing role in kinetic modeling. Thus minimizing the uncertainty of theoretical prediction across wide working conditions is crucial to refine a kinetic model. The present study takes ethyl (C2H5) + oxygen (O2) reaction system to show that combined forward and reverse uncertainty analysis can be used to further constrain calculated rate coefficients and branching ratios, which were already calculated by high‐level quantum chemistry methods. Forward global uncertainty analysis with the artificial neural network‐high dimensional model representation (ANN‐HDMR) method is employed to select key parameters affecting total rate coefficients of C2H5 + O2 and branching ratios of C2H5 + O2 = C2H4 + HO2 (C1). Reverse uncertainty analysis with Bayesian method was then applied to refine the key input parameters based on experimental data at working conditions selected by sensitivity entropy. Although the target RRKM/ME model system was built on high level theoretical calculations, the combined forward and reverse uncertainty analyses are still able to reduce uncertainties of predicted total rate coefficients of C2H5 + O2 and branching ratios for C1 across a wide range of working conditions. Specifically, the uncertainties of total rate coefficient and C1 branching ratio have been reduced from 1.46 and 1.52 to 1.30 and 1.36 at 298 K and 1 Torr. The analysis process proposed in the present work effectively extrapolates the constraint ability of accurate measured data at one condition to wide working conditions based on the RRKM/ME model.

Multistate Dynamics and Kinetics of CO2 Activation by Ta+ in the Gas Phase: Insights into Single-Atom Catalysis.

The activation of carbon dioxide (CO2) by a transition-metal cation in the gas phase is a unique model system for understanding single-atom catalysis. The mechanism of such reactions is often attributed to a "two-state reactivity" model in which the high-energy barrier of a spin state correlating with ground-state reactants is avoided by intersystem crossing (ISC) to a different spin state with a lower barrier. However, such a "spin-forbidden" mechanism, along with the corresponding dynamics, has seldom been rigorously examined theoretically, due to the lack of global potential energy surfaces (PESs). In this work, we report full-dimensional PESs of the lowest-lying quintet, triplet, and singlet states of the TaCO2+ system, machine-learned from first-principles data. These PESs and the corresponding spin-orbit couplings enable us to provide an extensive theoretical characterization of the dynamics and kinetics of the reaction between the tantalum cation (Ta+) and CO2, which have recently been investigated experimentally at high collision energies using crossed beams and velocity map imaging, as well as at thermal energies using a selected-ion flow tube apparatus. The multistate quasi-classical trajectory simulations with surface hopping reproduce most of the measured product translational and angular distributions, shedding valuable light on the nonadiabatic reaction dynamics. The calculated rate coefficients from 200 to 600 K are also in good agreement with the latest experimental measurements. More importantly, these calculations revealed that the reaction is controlled by intersystem crossing, rather than potential barriers.

Semi-empirical cross-section formulas for electron-impact ionization and rate coefficient calculations

We propose a semi-empirical formula for the cross section of ionization by electron impact. The formula involves adjustable parameters which are determined by comparison with measured or numerically calculated cross sections. In the latter case, the ions are perturbed by their environment which is a high-density plasma. As a consequence, the cross section is significantly modified. We investigate Be-like carbon, nitrogen and oxygen as well as aluminum ions. We also show that the formula is well-suited for interpolation and extrapolation. Knowing the cross section, we calculate the rate coefficient within the Boltzmann and Fermi–Dirac statistics. In the first case, the rate can be calculated analytically. In the second one, it can be expressed in terms of special functions, but the numerical evaluation is more convenient while providing accurate results. Our results are compared to experiment and to other calculations.

Experimental and Theoretical Study of the OH-Initiated Degradation of Piperidine under Simulated Atmospheric Conditions.

The OH-initiated photo-oxidation of piperidine and the photolysis of 1-nitrosopiperidine were investigated in a large atmospheric simulation chamber and in theoretical calculations based on CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The rate coefficient for the reaction of piperidine with OH radicals was determined by the relative rate method to be kOH-piperidine = (1.19 ± 0.27) × 10-10 cm3 molecule-1 s-1 at 304 ± 2 K and 1014 ± 2 hPa. Product studies show the piperidine + OH reaction to proceed via H-abstraction from both CH2 and NH groups, resulting in the formation of the corresponding imine (2,3,4,5-tetrahydropyridine) as the major product and in the nitramine (1-nitropiperidine) and nitrosamine (1-nitrosopiperidine) as minor products. Analysis of 1-nitrosopiperidine photolysis experiments under natural sunlight conditions gave the relative rates jrel = j1-nitrosoperidine/jNO2 = 0.342 ± 0.007, k3/k4a = 0.53 ± 0.05 and k2/k4a = (7.66 ± 0.18) × 10-8 that were subsequently employed in modeling the piperidine photo-oxidation experiments, from which the initial branchings between H-abstraction from the NH and CH2 groups, kN-H/ktot = 0.38 ± 0.08 and kC2-H/ktot = 0.49 ± 0.19, were derived. All photo-oxidation experiments were accompanied by particle formation that was initiated by the acid-base reaction of piperidine with nitric acid. Primary photo-oxidation products including both 1-nitrosopiperidine and 1-nitropiperidine were detected in the particles formed. Quantum chemistry calculations on the OH initiated atmospheric photo-oxidation of piperidine suggest the branching in the initial H-abstraction routes to be ∼35% N1, ∼50% C2, ∼13% C3, and ∼2% C4. The theoretical study produced an atmospheric photo-oxidation mechanism, according to which H-abstraction from the C2 position predominantly leads to 2,3,4,5-tetrahydropyridine and H-abstraction from the C3 position results in ring opening followed by a complex autoxidation, of which the first few steps are mapped in detail. H-abstraction from the C4 position is shown to result mainly in the formation of piperidin-4-one and 2,3,4,5-tetrahydropyridin-4-ol, whereas H-abstraction from N1 under atmospheric conditions primarily leads to 2,3,4,5-tetrahydropyridine and in minor amounts of 1-nitrosopiperidine and 1-nitropiperidine. The calculated rate coefficient for the piperidine + OH reaction agrees with the experimental value within 35%, and aligning the theoretical numbers to the experimental value results in k(T) = 2.46 × 10-12 × exp(486 K/T) cm3 molecule-1 s-1 (200-400 K).

Improved Approach for ab Initio Calculations of Rate Coefficients for Secondary Reactions in Acrylate Free-Radical Polymerization.

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, β-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.

Collision induced molecular rotation of SiC4–He for astrophysical implications

ABSTRACT To probe the physical conditions in molecular clouds, observations of the rotational transitions of a molecular system are very important. Thus, accurate modelling of the emission spectra of silicon carbides requires the calculation of collision rate coefficients for its systems. We determine here, the collisional rate coefficients for the excitation of SiC4 by He using a new potential energy surface. The state-to-state rate coefficients between the lower levels (j ≤ 28) are calculated using the coupled-channel and coupled-state methods for temperatures ranging from 5 to 300 K. Finally, we model the excitation of the SiC4 radical in cold molecular clouds and star-forming regions using a radiative transfer model. For this purpose, the new rate coefficients are used to estimate the molecular abundances in interstellar clouds. Therefore, we recommend the use of this new data set in any astrophysical model of SiC4 radical excitation.

Theoretical study of the O(3P) + CN(X2Σ+) → CO(X1Σ+) + N(2D)/N(4S) reactions.

The barrierless exothermic reactions between atomic oxygen and the cyano radical, O(3P) + CN(X2Σ+) → CO(X1Σ+) + N(2D)/N(4S), play a significant role in combustion, astrochemistry, and hypersonic environments. In this work, their dynamics and kinetics are investigated using both wave packet (WP) and quasi-classical trajectory (QCT) methods on recently developed potential energy surfaces of the 12A', 12A,″ and 14A″ states. The product state distributions in the doublet pathway obtained with the WP method for a few partial waves show extensive internal excitation in the CO product. This observation, combined with highly oscillatory reaction probabilities, signals a complex-forming mechanism. The statistical nature of the reaction is confirmed by comparing the WP results with those from phase space theory. The calculated rate coefficients using the WP (with a J-shifting approximation) and QCT methods exhibit agreement with each other near room temperature, 1.77 × 10-10 and 1.31 × 10-10cm3molecule-1s-1, but both are higher than the existing experimental results. The contribution of the quartet pathway is small at room temperature due to a small entrance channel bottleneck. The QCT rate coefficients are further compared with experimental results above 3000K, and the agreement is excellent.

Fully relativistic distorted wave calculations of electron impact excitation of gallium atom: Cross sections relevant for plasma kinetic modeling

Electron impact excitation cross sections of neutral Ga are calculated using the relativistic distorted wave approximation with the aid of multiconfigurational Dirac-Fock wavefunctions. The cross sections are calculated from the fine structure resolved levels of the 4s24p manifold, i.e., from the ground 2P1/2 and the first excited state 2P3/2, to the fine structure resolved levels of the manifolds 4s24pdf, 4s4p2(4P1/2,4P3/2, and 4P5/2), 4s25spdf, 4s26spdf, 4s27spdf, and 4s28spdf for incident electron energies ranging from threshold to 500 eV. Where available, a comparison of the calculated oscillator strengths, transition probabilities, and cross sections with the previously reported results has been performed. The cross sections for the excitation from 4s24p2P1/2 to 4s24f, 4s4p2(4P1/2,4P3/2, and 4P5/2), 4s25f, 4s26f, 4s27df, and 4s28spdf and all the excitation cross sections from 4s24p2P3/2 are calculated and reported for the first time for a wide range of electron energies. Furthermore, the rate coefficients are also calculated using the present cross sections for an electron temperature varying from 0.5 to 5 eV. An analytic fitting of the calculated rate coefficients is provided to facilitate their inclusion in various plasma kinetic models.

Theoretical study on iso‐pentanol oxidation chemistry: Fuel radical isomerization and decomposition kinetics and mechanism development

AbstractThis study undertakes a detailed theoretical investigation into the iso‐pentanol radical isomerization and decomposition kinetics and the mechanism development of the iso‐pentanol oxidation. The CCSD(T)/CBS//M08‐HX/6‐311+G(2df,2p) method was adopted to calculate the reaction potential energy surface. The reaction rate coefficients were calculated by variational transition state theory (VTST) with multistructural torsional (MS‐T) partition function and small curvature tunneling (SCT) correction. Moreover, the pressure‐dependent rate coefficients were determined using the system‐specific quantum Rice‐Ramsperger‐Kassel theory (SS‐QRRK). The variational and tunneling effects were discussed, and the dominant reaction channels were identified. It reveals that the isomerization reactions play a significant role at low temperatures, while the decomposition reactions dominate the high‐temperature regime. Notably, the quantitative rate expressions for iso‐pentanol radical decomposition reactions were also obtained. Furthermore, a new kinetic model incorporating the calculated rate coefficients was constructed, exhibiting satisfactory prediction performance on ignition delay times and improved predictive accuracy of species mole fractions. This work provides accurate rate data of isomerization and decomposition kinetics and contributes to a more comprehensive understanding of the iso‐pentanol oxidation mechanism.

The mechanism and kinetics of the atmospheric oxidation of CF3(CF2)2CHCH2 (HFC-1447fz) by hydroxyl radicals: ab initio investigation.

The oxidation of 3,3,4,4,5,5,5-heptafluoro-1-pentene (HFC-1447fz) by hydroxyl radicals plays a crucial role in atmospheric conditions. By employing the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level of theory, the detailed reaction mechanism, kinetics and atmospheric implications of the degradation of HFC-1447fz by hydroxyl radicals were investigated. Compared to H-abstraction channels, the OH addition reaction is determined to be more favorable initial pathways in the degradation processes of HFC-1447fz. The overall rate coefficient of the degradation of HFC-1447fz by OH radicals is estimated to be 1.66 × 10-12 cm3 molecule-1 s-1 and the lifetime of HFC-1447fz is found to be 7 days at 298 K, which are in good agreement with the reported experimental results. The global warming potential (GWP) for HFC-1447fz on the 50, 100 and 500-year time horizons is estimated using the calculated rate coefficient. Furthermore, the mechanisms of the subsequent reactions of two OH-addition adducts have also been investigated. By TD-DFT calculations, it was found that eleven species can undergo photodissociation, while ten other species are photolytically stable under sunlight.

Oxidation pathways and kinetics of the 1,1,2,3-tetrafluoropropene (CF2CF-CH2F) reaction with Cl-atoms and subsequent aerial degradation of its product radicals in the presence of NO.

To give a comprehensive account of the environmental acceptability of 1,1,2,3-tetrafluoropropene (CF2CF-CH2F) in the troposphere, we have examined the oxidation reaction pathways and kinetics of CF2CF-CH2F initiated by Cl-atoms using the second-order Møller-Plesset perturbation (MP2) theory along with the 6-31+G(d,p) basis set. We also performed single-point energy calculations to further refine the energies at the CCSD(T) level along with the basis sets 6-31+G(d,p) and 6-311++G(d,p). The estimation of the relative energies and thermodynamic parameters of the CF2CF-CH2F + Cl reaction clearly shows that Cl-atom addition reaction pathways are more dominant compared to H-abstraction reaction pathways. The value of the rate coefficient for each reaction channel is calculated using the conventional transition state theory (TST) over the temperature range of 200-1000 K at 1 atm. The estimated overall rate coefficients for the title reaction are found to be 1.10 × 10-12, 1.21 × 10-10, and 1.13 × 10-8 cm3 per molecule per s via the respective calculation methods viz. MP2/6-31+G(d,p), CCSD(T)//MP2/6-31+G(d,p), and CCSD(T)/6-311++G(d,p)//MP2/6-31+G(d,p), at 298.15 K. Moreover, the calculated rate coefficients and percentage branching ratio values suggest that the Cl-atom addition reaction at the β-carbon atom is more preferable to that of the α-carbon addition to CF2CF-CH2F. Based on the rate coefficient values calculated by the three different methods, the atmospheric lifetime for the title reaction at 298.15 K is estimated. The radiative efficiency (RE) and Global Warming Potential (GWP) results of the title molecule show that its GWP would be negligible. Further, we have explored the degradation of its product radicals in the presence of O2 and NO. From the degradation results, we have found that CF2(Cl)COF, FCOCH2F, FCFO and FCOCl are formed as stable end products along with various radicals such as ˙CF2Cl and ˙CH2F. Therefore, these findings of kinetic and mechanistic data can be applied to the development and implementation of a novel CFC replacement.

Oxepin Derivatives Formation from Gas-Phase Catechol Ozonolysis.

Quantum chemical calculations are performed to explore all of the possible pathways for primary ozonide (POZ) formation from gas-phase ozonolysis of catechol. Canonical transition state theory has been used to calculate the rate coefficients of individual steps for the formation of POZ. The calculated rate coefficients for 1,3-cycloaddition of ozone at the (i) unsaturated C(OH)═C(OH) bond and (ii) CH═C(OH) of catechol, respectively, are in good agreement with the experimental rate constant. In general, subsequent decomposition of POZ leads to well-known Criegee Intermediates. This work reveals a parallel pathway by which the endo-addition of ozone at CH═C(OH) of catechol proceeds through oxepin derivatives along with the paths leading to Criegee Intermediates and peroxy acids. The 7-membered heterocyclic oxepin derivatives have lower energies than Criegee Intermediates but similar relative energies with peroxy acids.

TRANSPORT CHARACTERISTICS OF ELECTRONS IN NITROUS OXIDE (N2O) UNDER THE INFLUENCE OF CROSSED ELECTRIC AND MAGNETIC DC FIELDS

Monte Carlo (MC) calculations of transport and rate coefficients of an electron swarm moving in nitrous oxide (N2O) under the influence of DC crossed electric and magnetic orthogonal fields are present- ed. The set of cross sections for e-/N2O scattering obtained in our previous investigations was used as the initial parameter. Calculations of mean energy, drift velocity, diffusion coefficients and rate coefficients for elastic and individual inelastic processes were performed for five different values of the reduced magnetic field (B/N = 100 Hx, 200 Hx, 500 Hx, 1000 Hx and 2000 Hx, 1Hx = 10-27 Tm3), where for each of these values, the value of the reduced electric field (E/N) ranged from 50 Td to 2000 Td (1Td = 10-21Vm2). The ratio of cyclotron to total collision frequency in these cases is less than one for all values of B/N (except for the highest one when it is slightly greater than one), so we may claim that our swarm is in a collision-domi- nated regime. The cooling effect of the swarm is observable, i.e. there is a decrease in its mean energy as the magnetic field increases, as well as a decrease in the drift velocity component in the electric field direction. Electron diffusion is slightly anisotropic for the higher values of B/N.

Can a single ammonia and water molecule enhance the formation of methanimine under tropospheric conditions?: kinetics of •CH2NH2 + O2 (+NH3/H2O).

The aminomethyl (•CH2NH2) radical is generated from the photo-oxidation of methylamine in the troposphere and is an important precursor for new particle formation. The effect of ammonia and water on the gas-phase formation of methanimine (CH2NH) from the •CH2NH2 + O2 reaction is not known. Therefore, in this study, the potential energy surfaces for •CH2NH2 + O2 (+NH3/H2O) were constructed using ab initio//DFT, i.e., coupled-cluster theory (CCSD(T))//hybrid-density functional theory, i.e., M06-2X with the 6-311++G (3df, 3pd) basis set. The Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) simulation with Eckart's asymmetric tunneling was used to calculate the rate coefficients and branching fractions relevant to the troposphere. The results show 40% formation of CH2NH at the low-pressure (<1 bar) and 100% formation of CH2NH2OO• at the high-pressure limit (HPL) condition. When an ammonia molecule is introduced into the reaction, there is a slight increase in the formation of CH2NH; however, when a water molecule is introduced into the reaction, the increase in the formation of CH2NH was from 40% to ∼80%. The calculated rate coefficient for •CH2NH2 + O2 (+NH3) [1.9 × 10-23cm3 molecule-1 s-1] and for CH2NH2 + O2 (+H2O) [3.3 × 10-17cm3 molecule-1 s-1] is at least twelve and six order magnitudes smaller than those for free •CH2NH2 + O2 (2 × 10-11cm3 molecule-1 s-1 at 298K) reactions, respectively. Our result is consistent with that of previous experimental and theoretical analysis and in good agreement with its isoelectronic analogous reaction. The work also provides a clear understanding of the formation of tropospheric carcinogenic compounds, i.e., hydrogen cyanide (HCN).

Abundance and excitation of molecular anions in interstellar clouds

We present new observations of molecular anions with the Yebes 40 m and IRAM 30 m telescopes toward the cold, dense clouds TMC-1 CP, Lupus-1A, L1527, L483, L1495B, and L1544. We report the first detections of C3N− and C5N− in Lupus-1A as well as C4H− and C6H− in L483. In addition, we detected new lines of C6H− toward the six targeted sources, of C4H− toward TMC-1 CP, Lupus-1A, and L1527, and of C8H− and C3N− in TMC-1 CP. Excitation calculations using recently computed collision rate coefficients indicate that the lines of anions accessible to radiotelescopes run from subthermally excited to thermalized as the size of the anion increases, with the degree of departure from thermalization depending on the H2 volume density and the line frequency. We noticed that the collision rate coefficients available for the radical C6H are not sufficient to explain various observational facts, thereby calling for the collision data for this species to be revisited. The observations presented here, together with observational data from the literature, have been used to model the excitation of interstellar anions and to constrain their abundances. In general, the anion-to-neutral ratios derived here agree with the literature values, when available, within 50% (by a factor of two at most), except for the C4H−/C4H ratio, which shows higher differences due to a revision of the dipole moment of C4H. From the set of anion-to-neutral abundance ratios derived two conclusions can be drawn. First, the C6H−/C6H ratio shows a tentative trend whereby it increases with increasing H2 density, as we would expect on the basis of theoretical grounds. Second, the assertion that the higher the molecular size, the higher the anion-to-neutral ratio is incontestable; furthermore, this supports a formation mechanism based on radiative electron attachment. Nonetheless, the calculated rate coefficients for electron attachment to the medium size species C4H and C3N are probably too high and too low, respectively, by more than one order of magnitude.

SiS formation in the interstellar medium via SiH + S collisions

ABSTRACT One of the most important Si-bearing species in the intersellar medium is the SiS molecule. Thermal rate coefficients and other collisional properties are calculated for its formation via the title reaction using the quasi-classical trajectory method. An accurate representation of the HSiS potential energy surface is employed, which has been modelled from high-level ab initio calculations and a reliable description of long-range interactions as implied by the underlying double many-body expansion method. The calculated rate coefficients for the $\rm SiH + S \rightarrow SiS + H$ reaction can be modelled with k(T) = α(T/300)βe−γ/T where $\alpha =0.63\times 10^{-10}\, \rm cm^3\, s^{-1}$, β = -0.11, and $\gamma = 11.6\, \rm K$. This result is only slightly lower than that for SiS formation via Si + SH collisions. The contribution of each reaction mechanism and the rovibrational energy distributions of the nascent SiS molecule are also calculated. The title collision can also yield SH ($\rm SiH + S \rightarrow SH + Si$), but the corresponding rate coefficient is 20 to 27 times smaller than for SiS formation ($\alpha =0.025\times 10^{-10}\rm cm^3\, s^{-1}$, β =-0.13, and $\gamma = 9.38\, \rm K$). The role of intersections between excited electronic states is also discussed, based on novel calculations including eight electronic states.