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The anions C |$_7$| N |$^-$| and C |$_{10}$| H |$^-$| are the two longest of the linear (C,N)-bearing and (C,H)-bearing chains that have so far been detected in the interstellar medium (ISM). In order to glean information on their collision-induced rotational state-changing processes, we analyse the general features of new ab initio potentials describing the interaction of both linear anions with H |$_2$|⁠ , one of the most abundant partners in their ISM environment. We employ an artificial neural network fit of the reduced-dimensionality potential energy surface for C |$_7$| N |$^-$|⁠...H |$_2$| interaction and discuss in detail the spatial features in terms of multipolar radial coefficients. For the C |$_{10}$| H |$^-$|⁠...H |$_2$| interaction, we use the initial grid of two-dimensional raw points to generate by quadrature the Legendre expansion directly, further including the long-range terms as discussed in the main text. Quantum scattering calculations are employed to obtain rotationally inelastic cross-sections, for collision energies in the range of 10 |$^{-4}$| to 400 cm |$^{-1}$|⁠. From them we generate the corresponding inelastic rate coefficients as a function of temperature covering the range from 10 to 50 K. The results for the rate coefficients for the longest cyanopolyyne are compared with the earlier results obtained for the smaller terms of the same series, also in collision with H |$_2$|⁠. We obtain that the inelastic rate coefficients for the long linear anions are all fairly large compared with the earlier systems. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are illustrated in our conclusions. [ABSTRACT FROM AUTHOR]

The anion C5N− is one of the largest linear (C,N)-bearing chains detected in the interstellar medium. Here we present and discuss the general features of new ab initio potential energy surfaces describing the interaction of this linear anion with He and H2. We employ a Legendre Polynomials expansion representation for the former and an artificial neural network fit for the latter. We then carry out quantum scattering calculations to yield rotationally inelastic cross-sections for collisions with He and H2, using relative translational energy values in the range of 0.1–300 cm−1. We then obtained the corresponding inelastic rate coefficients as a function of temperature covering the range from 1 to 100 K. The results for these two systems are compared with each other, as well as with the earlier results on the C3N− colliding with the same partners. We found that the final inelastic rate coefficients for this anion are all fairly large, those from collisions with H2 being the largest. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are discussed in our conclusions. [ABSTRACT FROM AUTHOR]

The anions C |$_7$| N |$^-$| and C |$_{10}$| H |$^-$| are the two longest of the linear (C,N)-bearing and (C,H)-bearing chains that have so far been detected in the interstellar medium (ISM). In order to glean information on their collision-induced rotational state-changing processes, we analyse the general features of new ab initio potentials describing the interaction of both linear anions with H |$_2$|⁠ , one of the most abundant partners in their ISM environment. We employ an artificial neural network fit of the reduced-dimensionality potential energy surface for C |$_7$| N |$^-$|⁠...H |$_2$| interaction and discuss in detail the spatial features in terms of multipolar radial coefficients. For the C |$_{10}$| H |$^-$|⁠...H |$_2$| interaction, we use the initial grid of two-dimensional raw points to generate by quadrature the Legendre expansion directly, further including the long-range terms as discussed in the main text. Quantum scattering calculations are employed to obtain rotationally inelastic cross-sections, for collision energies in the range of 10 |$^{-4}$| to 400 cm |$^{-1}$|⁠. From them we generate the corresponding inelastic rate coefficients as a function of temperature covering the range from 10 to 50 K. The results for the rate coefficients for the longest cyanopolyyne are compared with the earlier results obtained for the smaller terms of the same series, also in collision with H |$_2$|⁠. We obtain that the inelastic rate coefficients for the long linear anions are all fairly large compared with the earlier systems. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are illustrated in our conclusions. [ABSTRACT FROM AUTHOR]

The elementary mechanisms through which molecular polyynes could form stable negative ions after interacting with free electrons in planetary atmospheres (e.g., Titan's) are analyzed using quantum scattering calculations and quantum structure methods. The case of radical species and of nonpolar partners are analyzed via specific examples for both the CnH and HCnH series, with n values from 4 to 12. We show that attachment processes to polar radicals are dominating the anionic production and that the mediating role of dipolar scattering states is crucial to their formation. The corresponding attachment rates are presented as calculated upper limits to their likely values and are obtained down to the low temperatures of interest. The effects of the computed rates, when used in simple evolutionary models, are also investigated and presented in detail. [ABSTRACT FROM AUTHOR]

Chemistry plays a key role in the evolution of the interstellar medium, so it is highly important to follow its evolution in numerical simulations. However, it could easily dominate the computational cost when applied to large systems. In this paper we discuss two approaches to reduce these costs: (i) based on computational strategies, and (ii) based on the properties and on the topology of the chemical network. The first methods are more robust, while the second are meant to be giving important information on the structure of large, complex networks.We first discuss the numerical solvers for integrating the system of ordinary differential equations (ODE) associated with the chemical network, and then we propose a buffer method that decreases the computational time spent in solving the ODE system. We further discuss a flux-based method that allows one to determine and then cut on the fly the less active reactions.In addition we also present a topological approach for selecting the most probable species that will be active during the chemical evolution, thus gaining information on the chemical network that otherwise would be difficult to retrieve. This topological technique can also be used as an a priori reduction method for any size network.We implemented these methods into a 1D Lagrangian hydrodynamical code to test their effects: both classes lead to large computational speed-ups, ranging from ×2 to ×5. We have also tested some hybrid approaches finding that coupling the flux method with a buffer strategy gives the best trade-off between robustness and speed-up of calculations. [ABSTRACT FROM AUTHOR]

The time-dependent rate coefficients for the charge exchange reaction C+ + Si → C + Si+ for doublet and quartet states have been determined with ab initio quantum calculations coupled with a non-adiabatic transition model based on a simple Landau–Zener picture. This reaction plays a key role in determining the abundances of C, Si and their ions, in the interstellar medium since these abundances affect the fine-structure cooling and hence the star formation rates. We also provide additional calculations to evaluate the differences between the gas evolution as obtained by using the empirical rate estimates found in the current literature and the calculations presented in this work which are based on our more realistic evaluation of such rates from ab initio transition probabilities. We shall thus show here that the new rates yield important differences for metal-rich environments where T < 104 K and the ultraviolet flux is very small, while becoming less important at higher T values and higher photon fluxes. [ABSTRACT FROM AUTHOR]

The formation of anionic species in the interstellar medium from interaction of linear molecules containing carbon, nitrogen and hydrogen as atomic components (polyynes) with free electrons in the environment is modelled via a quantum treatment of the collision dynamics. The ensuing integral cross-sections are employed to obtain the corresponding attachment rates over a broad range of temperatures for the electrons. The calculations unequivocally show that a parametrization form often employed for such rates yields a broad range of values that turn out to be specific for each molecular species considered, thus excluding using a unique set for the whole class of polyynes. [ABSTRACT FROM PUBLISHER]

Context. The attachment of free electrons to polycondensed aromatic ring molecules (PAHs) is studied for the variety of these molecules with different numbers of condensed rings and over a broad range of electron temperatures, using a multichannel quantum scattering approach. The calculations of the relevant cross sections are used in turn to model the corresponding attachment rates for each of the systems under study, and these rates are parametrized as a function of temperature using a commonly employed expression for two-body processes in the interstellar medium (ISM). Aims. The scope of this work is to use first principles to establish the influence of chemical properties on the efficiency of the electronattachment process for PAHs. Methods. Quantum multichannel scattering methods are employed to generate the relevant cross sections, hence the attachment rates, using integral elastic cross sections computed over a broad range of relevant energies, from threshold up to 1000 K and linking the attachment to low-energy resonant collisions. Results. The rates obtained for the present molecules are found to markedly vary within the test ensemble of the present work and to be lower than the earlier values used for the entire class of PAHs anions, when modelling their evolutions in ISM environments. The effects of such differences on the evolutions of chemical networks that include both PAH and PAH-species are analysed in some detail and related to previous calculations. [ABSTRACT FROM AUTHOR]

ABSTRACT We present a new computational scheme aimed at reducing the complexity of the chemical networks in astrophysical models, one which is shown to markedly improve their computational efficiency. It contains a flux-reduction scheme that permits us to deal with both large and small systems. This procedure is shown to yield a large speed-up of the corresponding numerical codes and provides good accord with the full network results. We analyse and discuss two examples involving chemistry networks of the interstellar medium and show that the results from the present reduction technique reproduce very well the results from fuller calculations. [ABSTRACT FROM AUTHOR]

Free, gas-phase polycyclic aromatic hydrocarbons (PAHs) are understood to play an important role in the interstellar medium (ISM), as they are thought to significantly contribute to both diffused and unidentified infrared interstellar bands. They are also considered fundamental blocks of the interstellar dust, whose nature has important implications for a plethora of physical and chemical nanoscopic processes within the ISM. Since free electrons represent a versatile alternative way to transport energy in the interstellar space, in this paper we compute from quantum scattering methods the angular redistributions of free electrons by gas-phase coronene molecules, the latter of which are believed to be one of the most representative PAHs, in order to assess their role in describing the efficiency of electron deflection by this molecule. The associated rates can provide useful information about the coupling mechanism between external radio-frequency fields and complex molecular plasmas containing neutral and ionized PAHs. They can also yield information on the possible presence of such species in the dust phase of the medium. [ABSTRACT FROM AUTHOR]

The radiative association rates for the formation of LiHe+ molecules in their ground electronic state have been calculated employing an accurate ab initio potential energy curve and the dipole moment function. The enhancement of this rate, which may arise from stabilizing emissions stimulated by the cosmic background radiation field, has also been calculated and analyzed in the context of early universe conditions. Direct photodissociation processes have also been studied using local thermal equilibrium cross sections and rates are reported for temperatures between 600 and 9000 K. These photochemical processes are in turn analyzed and discussed as a function of the redshift ɀ that is expected to operate in the early universe chemical kinetics. All data suggest very low residual abundances of this molecule and therefore its marginal role within early universe chemistry. [ABSTRACT FROM AUTHOR]

The barrierless, exothermic reactions of H– with HCnN cyanopolyynes, with n = 1 and 3, are analyzed using ab initio calculations of the interaction forces. The shape of the reactive potential energy surface suggests the most efficient approach of H– to be on a nearly collinear arrangement on the H-side of HCnN. Using simple transition state formulation of the reaction rates, which are obtained via calculation of the partition functions of each transition state configuration, provides a new non-Langevin behavior of the reaction which can help explain the unexpectedly large density of CN– formation found in observations. A similar procedure is also employed for the reaction of H– with HC3N and the differences in the results, indicating a lower efficiency of the latter reactivity compared with that for CN–, are discussed in this paper. [ABSTRACT FROM AUTHOR]

The anion C5N− is one of the largest linear (C,N)-bearing chains detected in the interstellar medium. Here we present and discuss the general features of new ab initio potential energy surfaces describing the interaction of this linear anion with He and H2. We employ a Legendre Polynomials expansion representation for the former and an artificial neural network fit for the latter. We then carry out quantum scattering calculations to yield rotationally inelastic cross-sections for collisions with He and H2, using relative translational energy values in the range of 0.1–300 cm−1. We then obtained the corresponding inelastic rate coefficients as a function of temperature covering the range from 1 to 100 K. The results for these two systems are compared with each other, as well as with the earlier results on the C3N− colliding with the same partners. We found that the final inelastic rate coefficients for this anion are all fairly large, those from collisions with H2 being the largest. The consequences of such findings on their non-equilibrium rotational populations in interstellar environments are discussed in our conclusions. [ABSTRACT FROM AUTHOR]

A detailed analysis of an ionic reaction that plays a crucial role in the carbon chemistry of the interstellar medium (ISM) is carried out by computing ab initio reactive cross sections with a quantum method and by further obtaining the corresponding CH+ destruction rates over a range of temperatures that shows good overall agreement with existing experiments. The differences found between all existing calculations and the very-low-T experiments are discussed and explored via a simple numerical model that links these cross section reductions to collinear approaches where nonadiabatic crossing is expected to dominate. The new rates are further linked to a complex chemical network that models the evolution of the CH+ abundance in the photodissociation region (PDR) and molecular cloud (MC) environments of the ISM. The abundances of CH+ are given by numerical solutions of a large set of coupled, first-order kinetics equations that employs our new chemical package krome. The analysis that we carry out reveals that the important region for CH+ destruction is that above 100 K, hence showing that, at least for this reaction, the differences with the existing laboratory low-T experiments are of essentially no importance within the astrochemical environments discussed here because, at those temperatures, other chemical processes involving the title molecule are taking over. A detailed analysis of the chemical network involving CH+ also shows that a slight decrease in the initial oxygen abundance might lead to higher CH+ abundances because the main chemical carbon ion destruction channel is reduced in efficiency. This might provide an alternative chemical route to understand the reason why general astrochemical models fail when the observed CH+ abundances are matched with the outcomes of their calculations. [ABSTRACT FROM AUTHOR]