Collisional excitation of HC3N by para- and ortho-H2

New calculations for rotational excitation of cyanoacetylene by collisions with hydrogen molecules are performed to include the lowest 38 rotational levels of HC3N and kinetic temperatures to 300 K. Calculations are based on the interaction potential of Wernli et al. A&A, 464, 1147 (2007) whose accuracy is checked against spectroscopic measurements of the HC3N-H2 complex. The quantum coupled-channel approach is employed and complemented by quasi-classical trajectory calculations. Rate coefficients for ortho-H2 are provided for the first time. Hyperfine resolved rate coefficients are also deduced. Collisional propensity rules are discussed and comparisons between quantum and classical rate coefficients are presented. This collisional data should prove useful in interpreting HC3N observations in the cold and warm ISM, as well as in protoplanetary disks.Comment: 8 pages, 2 tables, 4 figures, accepted for publication in MNRA

New theoretical method for calculating the radiative association cross section of a triatomic molecule: Application to N2-H-

We present a new theoretical method to treat the atom diatom radiative association within a time independent approach. This method is an adaptation of the driven equations method developed for photodissociation. The bound states energies and wave functions of the molecule are calculated exactly and used to propagate the overlap with the initial scattering wave function. In the second part of this paper, this approach is applied to the radiative association of the N2H- anion. The main features of the radiative association cross sections are analysed and the magnitude of the calculated rate coefficient at 10 Kelvin is used to discuss the existence of the N2H- in the interstellar medium which could be used as a tracer of both N2 and H-

The rotational excitation of HCN and HNC by He: New insights on the HCN/HNC abundance ratio in molecular clouds

Modeling of molecular emission from interstellar clouds requires the calculation of rates for excitation by collisions with the most abundant species. The present paper focuses on the calculation of rate coefficients for rotational excitation of the HCN and HNC molecules in their ground vibrational state in collision with He. The calculations are based on new two-dimensional potential energy surfaces obtained from highly correlated \textit{ab initio} calculations. Calculations of pure rotational (de)excitation cross sections of HCN and HNC by He were performed using the essentially exact close-coupling method. Cross sections for transitions among the 8 first rotational levels of HCN and HNC were calculated for kinetic energies up to 1000 cm$^{-1}$. These cross sections were used to determine collisional rate constants for temperatures ranging from 5 K to 100 K. A propensity for even $\Delta j$ transitions is observed in the case of HCN--He collisions whereas a propensity for odd $\Delta j$ transitions is observed in the case of HNC--He collisions. The consequences for astrophysical models are evaluated and it is shown that the use of HCN rate coefficients to interpret HNC observations can lead to significant inaccuracies in the determination of the HNC abundance, in particular in cold dark clouds for which the new HNC rates show that the $j=1-0$ line of this species will be more easily excited by collisions than HCN. An important result of the new HNC-He rates is that the HNC/HCN abundance ratio derived from observations in cold clouds has to be revised from $>$1 to $\simeq$1, in good agreement with detailed chemical models available in the literature.Comment: 8 figue

Formation of interstellar SH+^+ from vibrationally excited H2_2: Quantum study of S+^+ + H2_2 ⇄\rightleftarrows SH+^+ + H reactions and inelastic collisions

The rate constants for the formation, destruction, and collisional excitation of SH$^+$ are calculated from quantum mechanical approaches using two new SH$_2^+$ potential energy surfaces (PESs) of $^4A''$ and $^2A''$ electronic symmetry. The PESs were developed to describe all adiabatic states correlating to the SH$^+$ ($^3\Sigma^-$) + H($^2S$) channel. The formation of SH$^+$ through the S$^+$ + H$_2$ reaction is endothermic by $\approx$ 9860 K, and requires at least two vibrational quanta on the H$_2$ molecule to yield significant reactivity. Quasi-classical calculations of the total formation rate constant for H$_2$($v=2$) are in very good agreement with the quantum results above 100K. Further quasi-classical calculations are then performed for $v=3$, 4, and 5 to cover all vibrationally excited H$_2$ levels significantly populated in dense photodissociation regions (PDR). The new calculated formation and destruction rate constants are two to six times larger than the previous ones and have been introduced in the Meudon PDR code to simulate the physical and illuminating conditions in the Orion bar prototypical PDR. New astrochemical models based on the new molecular data produce four times larger SH$^+$ column densities, in agreement with those inferred from recent ALMA observations of the Orion bar.Comment: 8 pages, 7 figure

Refit to numerically problematic UMIST reaction rate coefficients

Aims. Chemical databases such as the UMIST Database for Astrochemistry (UDFA) are indispensable in the numerical modeling of astrochemical networks. Several of the listed reactions in the UDFA have properties that are problematic in numerical computations: Some are parametrized in a way that leads to extremely divergent behavior for low kinetic temperatures. Other reactions possess multiple entries that are each valid in a different temperature regime, but have no smooth transition when switching from one to another. Numerically, this introduces many difficulties.We present corrected parametrizations for these sets of reactions in the UDFA06 database. Methods. From the tabulated parametrization in UDFA, we created artificial data points and used a Levenberg-Marquardt algorithm to find a set of improved fit parameters without divergent behavior for low temperatures. For reactions with multiple entries in the database that each possess a different temperature regime, we present one joint parametrization that is designed to be valid over the whole cumulative temperature range of all individual reactions. Results. We show that it is possible to parametrize numerically problematic reactions from UDFA in a form that avoids low temperature divergence. Additionally, we demonstrate that it is possible to give a collective parametrization for reaction rate coefficients of reactions with multiple entries in UDFA. We present these new fitted values in tabulated form.Comment: accepted by A&

Erratum to: The hyperfine excitation of OH radicals by He

Hyperfine-resolved collisions between OH radicals and He atoms are investigated using quantum scattering calculations and the most recent ab initio potential energy surface, which explicitly takes into account the OH vibrational motion. Such collisions play an important role in astrophysics, in particular in the modelling of OH masers. The hyperfine-resolved collision cross sections are calculated for collision energies up to 2500 cm-1 from the nuclear spin free scattering S-matrices using a recoupling technique. The collisional hyperfine propensities observed are discussed. As expected, the results from our work suggest that there is a propensity for collisions with ΔF = Δj. The new OH−He hyperfine cross sections are expected to significantly help in the modelling of OH masers from current and future astronomical observations

Hyperfine excitation of CN by para- and ortho-H2

Among the interstellar molecules, the CN radical is of particular interest since it is a good probe of cold dark molecular clouds, and especially prestellar cores. Modelling of CN emission spectra from these dense molecular clouds requires the calculation of rate coefficients for excitation by collisions with the most abundant species. We calculate fine- and hyperfinestructure-resolved excitation rate coefficients of CN(X2+) by para- and ortho-H2. The calculations are based on a new potential energy surface obtained recently from highly correlated ab initio calculations. State-to-state rate coefficients between fine and hyperfine levels of CN were calculated for low temperatures ranging from 5 to 100 K. The new results are compared to available CN rate coefficients. Significant differences are found between the different sets of rate coefficients. This comparison shows that the new CN–H2 rate coefficients have to be used for observations interpretations. We expect that their use will help significantly to have a new insight into the physical conditions of prestellar cores

New ab initio potential energy surfaces for the ro-vibrational excitation of OH(X-2 Pi) by He

International audienc

Collisional excitation of water by hydrogen atoms

We present quantum dynamical calculations that describe the rotational excitation of H$_2$O due to collisions with H atoms. We used a recent, high accuracy potential energy surface, and solved the collisional dynamics with the close-coupling formalism, for total energies up to 12 000 cm$^{-1}$. From these calculations, we obtained collisional rate coefficients for the first 45 energy levels of both ortho- and para-H$_2$O and for temperatures in the range T = 5-1500 K. These rate coefficients are subsequently compared to the values previously published for the H$_2$O / He and H$_2$O / H$_2$ collisional systems. It is shown that no simple relation exists between the three systems and that specific calculations are thus mandatory

Water mass properties derived from satellite observations in the Barents Sea

The Barents Sea is a region of deep water formation where Atlantic Water is converted into cooler, fresher Barents Sea Water. Barents Sea Water properties exhibit variability at seasonal, interannual, and decadal timescales. This variability is transferred to Arctic Intermediate Water, which eventually contributes to the deeper branch of the Atlantic meridional overturning circulation. Variations in Barents Sea Water properties are reflected in steric height (contribution of density to sea‐level variations) that depends on heat and freshwater contents and is a quantity usually derived from in situ observations of water temperature, salinity, and pressure that remain sparse during winter in the Barents Sea. This analysis explores the utility of satellite observations for representing Barents Sea Water properties and identifying trends and sources of variability through novel methods. We present our methods for combining satellite observations of eustatic height (the contribution of mass to sea‐level variations), sea surface height, and sea surface temperature, validated by in situ temperature and salinity profiles, to estimate steric height. We show that sea surface temperature is a good proxy for heat content in the upper part of the water column in the southeastern Barents Sea and that freshwater content can be reconstructed from satellite data. Our analysis indicates that most of the seasonality in Barents Sea Water properties arises from the balance between ocean heat transport and atmospheric heat flux, while its interannual variability is driven by heat and freshwater advection