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Investigating molecular excitation induced by collisions requires the prior determination of accurate analytical potential energy surfaces for the colliding partners. For carbon-chain molecules, such as cyanopolyynes, this has been a longstanding challenge, resulting in the absence of rate coefficients for HC5N, HC7N, HC9N, and others, induced by collisions with He. To overcome this bottleneck, we introduce a new approach: the Radial Angular Network with Gradual Expansion (RANGE). This method jointly connects the construction of ab initio interaction potentials with the determination of their analytical forms. We use the HC3N–He molecular complex as a reference to assess the reliability of our method, given that its analytical potential has been derived using various methods. Additionally, we apply the RANGE approach to construct the analytical representation of the interaction potential for HC5N–He and HC7N–He. The analysis of the analytical potentials reveals three systematic trends: (i) the anisotropy increases with the length of the carbon chain, (ii) the number of local minima correlates with the number of carbon atoms, and (iii) the shallowest local minimum is consistently located at ∼30 cm−1 below the dissociation limit of the complex. Using the time-independent quantum mechanical close-coupling formalism, we briefly estimate the propensity rules governing the excitation of HC3N, HC5N, and HC7N induced by collisions with He. Consequently, the three collisional systems exhibit the same propensity rule, favoring Δj = 2 transitions. [ABSTRACT FROM AUTHOR]

The cyclic form of magnesium dicarbide molecule (c-MgC |$_2$|⁠) has been detected in the carbon-rich circumstellar envelope of IRC+10216 and is considered as a valuable tracer for characterizing the physical conditions of the surrounding gas. In order to make the most of c-MgC |$_2$| observations and accurately derive the physical conditions of the media where c-MgC |$_2$| is detected, radiative transfer modelling, including collisional and radiative (de-)excitations, have to be performed. Here, we study the excitation of c-MgC |$_{2}$| induced by collisions with He (as a proxy for H |$_2$|⁠). A new 3D potential energy surface (PES) is constructed using highly correlated ab initio methods. This PES reveals a minimum with a well depth of 20.66 cm |$^{-1}$| below the c-MgC |$_2$| -He dissociation limit. Using this PES, we compute excitation cross sections for transitions between the low-lying rotational energy levels of c-MgC |$_2$| using the time-independent quantum mechanical close-coupling formalism. These cross sections are then thermally averaged over a Boltzmann energy distribution in order to derive excitation rate coefficients at low temperatures (⁠|$T \le 30$|  K). To evaluate the impact of these new rate coefficients on the interpretation of c-MgC |$_2$| observational spectra, we perform radiative transfer calculations. We find that a very high gas density (⁠|$n \gt 10^6$| cm |$^{-3}$|⁠) is needed in order for the collisional excitation to compete with the radiative de-excitation. We also find that the excitation temperatures of the observed lines predicted by our model differ by a factor two from the value derived from the observations in IRC+10216 circumstellar envelope, indicating that the excitation of c-MgC |$_{2}$| may also be driven by a strong radiative pumping in such media. Therefore, a more sophisticated non-LTE modelling, that takes into account the collisional and radiative excitations as well as the radiative pumping, is required to accurately interpret the observational spectra of c-MgC |$_2$|⁠. [ABSTRACT FROM AUTHOR]

Protonated molecules have been increasingly detected in the interstellar medium (ISM), and usually astrochemical models fail at reproducing the abundances derived from observational spectra. Rigorous interpretation of the detected interstellar emission lines requires prior calculations of collisional rate coefficients with H2 and He, i.e., the most abundant species in the ISM. In this work, we focus on the excitation of HCNH+ induced by collision with H2 and He. Therefore, we first calculate ab initio potential energy surfaces (PESs) using the explicitly correlated and standard coupled cluster method with single, double, and non-iterative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta basis set. Both the HCNH+–H2 and HCNH+–He potentials are characterized by deep global minima of 1426.60 and 271.72 cm−1, respectively, and large anisotropies. From these PESs, we derive state-to-state inelastic cross sections for the 16 low-lying rotational energy levels of HCNH+ using the quantum mechanical close-coupling approach. The differences between cross sections due to ortho- and para-H2 impacts turn out to be minor. Using a thermal average of these data, we retrieve downward rate coefficients for kinetic temperatures of up to 100 K. As it could be anticipated, differences of up to two orders of magnitude exist between the rate coefficients induced by H2 and He collisions. We expect that our new collision data will help to improve the disagreement between abundances retrieved from observational spectra and astrochemical models. [ABSTRACT FROM AUTHOR]

Due to the lack of specific collisional data, the abundance of NS+ in cold dense interstellar clouds was determined using collisional rate coefficients of CS as a substitute. To better understand the chemistry of sulfur in the interstellar medium, further abundance modeling using the actual NS+ collisional rate coefficients is needed. For this purpose, we have computed the first full 4D potential energy surface of the NS+–H2 van der Waals complex using the explicitly correlated coupled cluster approach with single, double, and non-iterative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta basis set. The potential energy surface exhibits a global minimum of 848.24 cm−1 for a planar configuration of the complex. The long-range interaction energy, described using multipolar moments, is sensitive to the orientation of H2 up to radial distances of ∼50 a0. From this new interaction potential, we derived excitation cross sections, induced by collision with ortho- and para-H2, for the 15 low-lying rotational levels of NS+ using the quantum mechanical close-coupling approach. By thermally averaging these data, we determined downward rate coefficients for temperatures up to 50 K. By comparing them with the previous NS+–H2 data, we demonstrated that reduced dimensional approaches are not suited for this system. In addition, we found that the CS collisional data underestimate our results by up to an order of magnitude. The differences clearly indicate that the abundance of NS+, in cold dense clouds retrieved from observational spectra, must be reassessed using these new collisional rate coefficients. [ABSTRACT FROM AUTHOR]

Tricarbon and pentacarbon monoxides have been detected towards the Taurus Molecular Cloud (TMC-1) with relatively important abundances. Understanding the chemical formation of these molecules requires interpreting their observational spectra by mean of non-local thermodynamical equilibrium modelling. For this purpose, we report rate coefficients of  C3O and  C5O induced by collision with He for temperatures up to 100 K. These data are obtained by calculating inelastic cross sections for the 31 low-lying rotational levels of  C3O and  C5O using the close-coupling approach. The comparison of the new rate coefficients with those of HC3N and HC5N, previously used to interpret the observational spectra of  C3O and  C5O, reveals differences of up to an order of magnitude. The effect of the new collisional rate coefficients in radiative transfer calculations is checked by computing the excitation temperatures for some transitions and simulating the  C3O and  C5O column densities observed towards TMC-1. Our findings suggest that the use of HC n N as template for C n O may lead to local thermodynamic equilibrium conditions for gas densities as low as ∼103  cm−3. Regarding the interpretation of the observational spectra, using radiative transfer modelling based on the actual C n O collisional rate coefficients instead of rotational diagram analysis leads to underestimate the column densities reported in the literature by up to 25 per cent and accordingly the  C3O/ C5O abundance ratio by up to 50 per cent. We expect that the new rate coefficients and the radiative transfer calculations presented in this work will encourage further modellings of the C n O abundance and accordingly constrain the chemistry. [ABSTRACT FROM AUTHOR]

Collisional energy transfer under cold conditions is of great importance from the fundamental and applicative point of view. Here, we investigate low temperature collisions of the SH- anion with He. We have generated a three-dimensional potential energy surface (PES) for the SH-(X¹Σ+)-He(¹S) van der Waals complex. The ab initio multi-dimensional interaction PES was computed using the explicitly correlated coupled cluster approach with simple, double, and perturbative triple excitation in conjunction with the augmented-correlation consistent-polarized valence triple zeta Gaussian basis set. The PES presents two minima located at linear geometries. Then, the PES was averaged over the ground vibrational wave function of the SH- molecule and the resulting two-dimensional PES was incorporated into exact quantum mechanical close coupling calculations to study the collisional excitation of SH- by He. We have computed inelastic cross sections among the 11 first rotational levels of SH- for energies up to 2500 cm-1. (De-)excitation rate coefficients were deduced for temperatures ranging from 1 to 300 K by thermally averaging the cross sections. We also performed calculations using the new PES for a fixed internuclear SH- distance. Both sets of results were found to be in reasonable agreement despite differences existing at low temperatures confirming that accurate predictions require the consideration of all internal degrees of freedom in the case of molecular hydrides. The rate coefficients presented here may be useful in interpreting future experimental work on the SH- negative ion colliding with He as those recently done for the OH- -He collisional system as well as for possible astrophysical applications in case SH- would be detected in the interstellar medium. [ABSTRACT FROM AUTHOR]

The recent detections of CNCN and HNCCN+ are seen as further evidence of the large abundance of NCCN in the interstellar medium. The accurate determination of the abundance of these chemically related compounds from the observational spectra requires the prior calculation of collisional rate coefficients. In this work, we aimed at computing hyperfine resolved rate coefficients for the CNCN–He collisional system. First, we determined a new potential energy surface for the CNCN–He van der Waals complex from which we computed rotationally resolved excitation cross-sections for energies up to 800 cm−1 using the quantum mechanical close-coupling approach. Then, hyperfine resolved transitions between the 30 low-lying pure rotational levels of CNCN were computed for temperatures ranging from 5 to 150 K using an improved infinite order sudden approach. The analysis of the scattering results showed a propensity rule in favour of Δ j  = Δ F 1 = Δ F for the hyperfine transitions and a slight dominance of the odd Δ j transitions. Using these data, we carried out non-LTE radiative transfer calculations to simulate the excitation of CNCN in molecular clouds and to constrain the physical conditions of cold dark clouds. Preliminary results showed that the abundance of CNCN derived from observational spectra has to be revisited using these new collisional data. [ABSTRACT FROM AUTHOR]