arXiv subjects

F. A. Gianturco

Publications and source records attributed to F. A. Gianturco.

At least 19 recordsLinked to original sources

arXiv2024

Rotationally inelastic rate coefficients for C$_7$N$^{-}$ and C$_{10}$H$^{-}$ anions in collision with H$_2$ at interstellar conditions

The anions C$_7$N$^-$ and C$_{10}$H$^-$ are the two longest of the linear (C,N)-bearing and (C,H)-bearing chains which have so far been detected in the Interstellar Medium. 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.

astro-ph.GA↗

arXiv2023

Computed Rotational Collision Rate Coefficients for Recently Detected Anionic Cyanopolyynes

We report new results from quantum calculations of energy-transfer processes taking place in interstellar environments and involving two newly observed molecular species: C$_5$N$^-$ and C$_7$N$^-$ in collision with He atoms and the p-H$_2$ molecules. These species are part of the anionic molecular chains labeled as cyanopolyynes which have been observed over the years in molecule-rich Circumstellar Envelopes and in molecular clouds. In the present work, we first carry out new $ab$ $initio$ calculations for the C$_7$N$^-$ interaction potential with He atom and then obtain state-to-state rotationally inelastic cross sections and rate coefficients involving the same transitions which have been observed experimentally by emission in the interstellar medium (ISM) from both of these linear species. For the C$_5$N$^-$/He system we extend the calculations already published in our earlier work (see reference below) to compare more directly the two molecular anions. We extend further the quantum calculations by also computing in this work collision rate coefficients for the hydrogen molecule interacting with C5N$^-$, using our previously computed interaction potential. Additionally, we obtain the same rate coefficients for the C$_7$N$^-$/H$_2$ system by using a scaling procedure that makes use of the new C$_7$N$^-$/He rate coefficients, as discussed in detail in the present paper. Their significance in affecting internal state populations in ISM environments where the title anions have been found is analyzed by using the concept of critical density indicators. Finally, similarities and differences between such species and the comparative efficiency of their collision rate coefficients are discussed. These new calculations suggest that, at least for the case of these longer chains, the rotational populations could reach local thermal equilibrium conditions within their observational environments.

astro-ph.GA↗

arXiv2020

Modeling ionic reactions at interstellar temperatures: the case of NH2- + H2 <--> NH3 + H-

We present in this paper the main structural features and enthalpy details for the energy profiles of the title reactions, both for the exothermic (forward) path to NH$_{3}$ formation and for the endothermic (reverse) reaction to NH$_{2}^{-}$ formation. Both systems have relevance for the nitrogen chemistry in the interstellar medium (ISM). They are also helpful to document the possible role of H$^{-}$ in molecular clouds at temperatures well below room temperature. The structural calculations are carried out using ab initio methods and are further employed to obtain the reaction rates down to the interstellar temperatures detected in earlier experiments. The reaction rates are obtained from the computed Minimum Energy Path (MEP) using the Variational Transition State Theory (VTST) approach. The results indicate very good accord with the experiments at room temperature, while the measured low temperature data down to 8 K are well described once we analyse in detail the physics of the reactions and modify accordingly the VTST approach. This is done by employing a T-dependent scaling, from room temperature conditions down to the lower ISM temperatures, which acknowledges the non-canonical behavior of the fast, barrierless exothermic reaction. This feature was also suggested in the earlier work discussed below in our main text. The physical reasons for the experimental behavior, and the need for improving on the VTST method when used away from room temperatures, are discussed in detail.

physics.chem-ph↗

arXiv2020

Collisional cooling of internal rotation in MgH$^+$ ions trapped with He atoms: Quantum modeling meets experiments in Coulomb crystals

Using the ab initio computed Potential Energy Surface (PES) for the electronic interaction of the MgH$^+$ ($^1Σ$) ion with the He($^1$S) atom, we calculate the relevant state-changing rotationally inelastic collision cross sections from a quantum treatment of the multichannel scattering problem. We focus on the quantum dynamics at the translationally low energies for the present partners discussed in the earlier, cold ion trap experiments (see below) which we wish to model in detail. The corresponding state-changing rates computed between the lower rotational states of the molecular ion are employed to describe the time-evolution kinetics followed by recent experiments on Coulomb-crystalized MgH$^+$ ($^1Σ$), where the ions are rotationally cooled by micromotion tuning after the uploading into the trap of He as a buffer gas. The present computational modeling of the final ions' rotational temperatures in the experiments turns out to agree very well with their observations and points at a fast equilibration between rotational and thermal temperatures of the ions.

physics.atom-ph↗

arXiv2019

Rotational state-changing collisions between N$_2^+$ and Rb at low energies

We present a theoretical study of rotationally elastic and inelastic collisions between molecular nitrogen ions and Rb atoms in the sub-Kelvin temperature regime prevalent in ion-atom hybrid trapping experiments. The cross sections for rotational excitation and de-excitation collisions were calculated using quantum-scattering methods on ab-initio potential energy surfaces for the energetically lowest singlet electronic channel of the system. We find that the rotationally inelastic collision rates are at least an order of magnitude smaller than the charge-exchange rates found in this system, rendering inelastic processes a minor channel under the conditions of typical hybrid trapping experiments.

physics.chem-ph↗

arXiv2018

Collisional state-changing of OH$^-$ rotations by interaction with Rb atoms in cold traps

We employ an accurate, ab initio potential energy surface (PES) which describes the electronic interaction energy between the molecular anion OH$^-$ ($^1Σ^+$) and the neutral rubidium atom Rb ($^2S$), to evaluate the elastic and inelastic cross sections over a range of energies representative of the conditions of low-T experiments in MOT traps, when combined with laser-cooled rubidium gas. The system is considered to be in its vibrational ground state, while the first four rotational levels are taken to be involved in the cooling and heating collisional processes that are computed here. The corresponding cooling and heating rates up to about 35 K are obtained from the calculations and compared with the recent results in a similar experiments, where He was the partner atom of the current anion.

physics.atom-ph↗

arXiv2018

Exploring a dynamical path for C$_2$H$^-$ and NCO$^-$ formation in dark molecular clouds

This paper deals with the possible formation of two molecular anions often considered likely components in the physical environments of the Interstellar Medium ( ISM) : $\mathrm{C_2H^-}$ and $\mathrm{NCO^-}$. They are both discussed here by computationally following the radiative association (RA) mechanism starting from $\mathrm{C_2^-}$, $\mathrm{H}$, $\mathrm{NC^-}$ and $\mathrm{O}$ as partners. The corresponding RA total cross sections produced by the calculations are in turn employed to generate the overall association rates over the relevant range of temperatures. The latter are found to be in line with other molecular ions formed by RA but not large enough to uniquivocally suggest this path as the main route to the anions formation in the ISM. Other possible paths of formation are also analysed and discussed. The presence of resonant structures during the association dynamics for both systems is found by the calculations and their consequences are discussed in some detail in the present study.

physics.chem-ph↗

arXiv2018

Formation of anionic C,N-bearing chains in the Interstellar medium via reactions of H$^{-}$ with HC$_x$N for odd-valued x from 1 to 7

We investigate the relative efficiencies of low-temperature chemical reactions in the Interstellar medium (ISM) with H$^-$ anion reacting in the gas phase with cyanopolyyne neutral molecules, leading to the formation of anionic C$_x$N$^-$ linear chains of different length and of H$_2$. All the reactions turn out to be without barriers, highly exothermic reactions which provide a chemical route to the formation of anionic chains of the same length . Some of the anions have been observed in the dark molecular clouds and in the diffuse interstellar envelopes.Quantum calculations are carried for the corresponding reactive potential energy surfaces (RPESs) for all the odd-numbered members of the series (x=1, 3, 5, 7). We employ the Minimum Energy paths (MEPs) to obtain the relevant Transition State (TS) configurations and use the latter within the Variational Transition State ( VTS) model to obtain the chemical rates. The present results indicate that, at typical temperatures around 100 K, a set of significantly larger rate values exists for x=3 and x=5, while are smaller for CN$^-$ and C$_7$N$^-$. At those temperatures, however, all the rates turn out to be larger than the estimates in the current literature for the Radiative Electron Attachment (REA) rates, thus indicating the greater importance of the present chemical path with respect to REA processes at those temperatures. The physical reasons for our findings are discussed in detail and linked with the existing observational findings.

physics.chem-ph↗

arXiv2018

Investigating the electronic properties and structural features of MgH and of MgH$^{-}$ anions

In the present paper we analyze in detail several properties of the MgH$^-$ anion and the MgH neutral molecule using accurate ab initio quantum computational methods in order to establish with higher reliability specific molecular features like the gas-phase electron affinity (EA) , the Frank-Condon (FC) factors for excitation of the neutral and of its anion to their lower electronic states, and the general feasibility of employing the anion in photodetachment experiments after its confinement in cold ion traps. The calculations suggest that the EA value is in agreement with an existing early experiment and further places on it a smaller error bar than that given before. Accurate zero-point-energy (ZPE) corrections are also included in our calculations and their effects discussed.

physics.atom-ph↗

arXiv2017

The H$_2$$^+$ + He proton transfer reaction: quantum reactive differential cross sections linked with velocity mappings

We construct the velocity map images of the proton transfer reaction between helium and molecular hydrogen ions H2+. We perform simulations of imaging experiments at one representative total collision energy taking into account the inherent aberrations of the velocity mapping in order to explore the feasibility of direct comparisons between theory and future experiments planned in our laboratory. The asymptotic angular distributions of the fragments in a 3D velocity space is determined from the quantum state-to-state differential reactive cross sections and reaction probabilities which are computed by using the time-independent coupled channel hyperspherical coordinate method. The calculations employ an earlier ab initio potential energy surface computed at the FCI/cc-pVQZ level of theory. The present simulations indicate that the planned experiments would be selective enough to differentiate between product distributions resulting from different initial internal states of the reactants.

physics.chem-ph↗

arXiv2016

Modeling the role of electron attachment rates on column density ratios for CnH-/CnH (n=4,6,8) in dense molecular clouds

(abridged) The fairly recent detection of a variety of anions in the Interstellar Molecular Clouds have underlined the importance of realistically modeling the processes governing their abundance. To this aim, our earlier calculations for the radiative electron attachment (REA) rates for C4H-, C6H-, and C8H- are employed to generate the corresponding column density ratios of anion/neutral (A/N) relative abundances. The latter are then compared with those obtained from observational measurements. The calculations involved the time-dependent solutions of a large network of chemical processes over an extended time interval and included a series of runs in which the values of REA rates were repeatedly scaled. Macroscopic parameters for the clouds' modeling were also varied to cover a broad range of physical environments. It was found that, within the range and quality of the processes included in the present network,and selected from state-of-the-art astrophysical databases, the REA values required to match the observed A/N ratios needed to be reduced by orders of magnitude for C4H- case, while the same rates for C6H- and C8H- only needed to be scaled by much smaller factors. The results suggest that the generally proposed formation of interstellar anions by REA mechanism is overestimated by current models for the C4H- case, for which is likely to be an inefficient path to formation. This path is thus providing a rather marginal contribution to the observed abundances of C4H-, the latter being more likely to originate from other chemical processes in the network, as we discuss in some detail in the present work.Possible physical reasons for the much smaller differences against observations found instead for the values of the (A/N) ratios in two other, longer members of the series are put forward and analyzed within the evolutionary modeling discussed in the present work.

astro-ph.GA↗

arXiv2014

KROME - a package to embed chemistry in astrophysical simulations

Chemistry plays a key role in many astrophysical situations regulating the cooling and the thermal properties of the gas, which are relevant during gravitational collapse, the evolution of disks and the fragmentation process. In order to simplify the usage of chemical networks in large numerical simulations, we present the chemistry package KROME, consisting of a Python pre-processor which generates a subroutine for the solution of chemical networks which can be embedded in any numerical code. For the solution of the rate equations, we make use of the high-order solver DLSODES, which was shown to be both accurate and efficient for sparse networks, which are typical in astrophysical applications. KROME also provides a large set of physical processes connected to chemistry, including photochemistry, cooling, heating, dust treatment, and reverse kinetics. The package presented here already contains a network for primordial chemistry, a small metal network appropriate for the modelling of low metallicities environments, a detailed network for the modelling of molecular clouds, a network for planetary atmospheres, as well as a framework for the modelling of the dust grain population. In this paper, we present an extended test suite ranging from one-zone and 1D-models to first applications including cosmological simulations with ENZO and RAMSES and 3D collapse simulations with the FLASH code. The package presented here is publicly available at http://kromepackage.org/ and https://bitbucket.org/krome/krome_stable

astro-ph.GA↗

arXiv2013

CH+ depletion by atomic hydrogen: accuracy of new rates in photo-dominated and self-shielded environments

A detailed quantum analysis of a ionic reaction with a crucial role in the ISM is carried out to generate ab initio reactive cross sections with a quantum method. From them we obtain the corresponding CH+ depletion rates over a broad range of temperatures. The new rates are further linked to a complex chemical network that shows the evolution in time of the CH+ abundance in photodissociation region (PDR) and molecular cloud (MC) environments. The evolutionary abundances of CH+ are given by numerical solutions of a large set of coupled, first-order kinetics equations by employing the new chemical package KROME. The differences found between all existing calculations from low-T experiments are explained via a simple numerical model that links the low-T cross section reductions to collinear approaches where nonadiabatic crossings dominate. The analysis of evolutionary abundance of CH+ reveals that the important region for the depletion reaction of this study is that above 100 K, hence showing that, at least for this reaction, the differences with the existing low-temperature experiments are of essentially no importance within the astrochemical environments. 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+ abundance since the main chemical carbon ion depletion channel is reduced in efficiency. This simplified observation might provide an alternative starting point to understand the problem of astrochemical models in matching the observed CH+ abundances.

astro-ph.GA↗

arXiv2013

Chemical complexity in astrophysical simulations: optimization and reduction techniques

Chemistry has a key role in the evolution of the interstellar medium (ISM), so it is highly desirable to follow its evolution in numerical simulations. However, it may 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. To this aim we first discuss the numerical solvers for integrating the system of ordinary differential equations (ODE) associated with the chemical network. We then 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 x2 to x5. 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.

astro-ph.IM↗

arXiv2012

Electron attachment rates for PAH anions in the ISM and dark molecular clouds: dependence on their chemical properties

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). AIM: The scope of this work is to use first principles to establish the influence of chemical properties on the efficiency of the electron-attachment 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.

astro-ph.GA↗

arXiv2012

Carbon Cations and Silicon Atoms in the ISM: modeling their charge exchange reaction

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 ISM 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 $T<10^4$ K and the UV flux is almost negligible, while becoming less important at higher T values and higher photon fluxes.

astro-ph.GA↗

arXiv2012

Electron-attachment rates for carbon-rich molecules in protoplanetary atmospheres: the role of chemical differences

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.

astro-ph.GA↗

arXiv2012

Complexity reduction of astrochemical networks

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 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.

astro-ph.IM↗