Engineering topics

Lique, François

Publications and source records attributed to Lique, François.

5 records

DOE OSTI2021

Inelastic rate coefficients for collisions of C 4 H - with H 2

Carbon-chain anions were recently detected in the interstellar medium. These very reactive species are used as tracers of the physical and chemical conditions in a variety of astrophysical environments. However, the local thermodynamic equilibrium conditions are generally not fulfilled in these environments. Therefore, collisional as well as radiative rates are needed to accurately model the observed emission lines. We determine in this work the state-to-state rate coefficients of C 4 H- in collision with both ortho- and para-H 2 . A new ab initio 4D potential energy surface was computed using explicitly correlated coupled-cluster procedures. This surface was then employed to determine rotational excitation and de-excitation cross-sections and rate coefficients for the first 21 rotational levels (up to rotational level j 1 = 20) using the close-coupling method, while the coupled-state approximation was used to extend the calculations up to j 1 = 30. State-to-state rate coefficients were obtained for the temperature range 2–100K. The differences between the ortho- and para-H 2 rate coefficients are found to be small.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2021

Inelastic scattering in isotopologues of O 2 –Ar: the effects of mass, symmetry, and density of states

The two species considered here, O 2 (oxygen molecule) and Ar (argon-atom), are both abundant components of Earth's atmosphere and hence familiar collision partners in this medium. O 2 is quite reactive and extensively involved in atmospheric chemistry, including Chapman's cycle of the formation and destruction of ozone; while Ar, like N 2 , typically plays the nevertheless crucial role of inert collider. Inert species can provide stabilization to metastable encounter-complexes through the energy transfer associated with inelastic collisions. The interplay of collision frequency and energy transfer efficiency, with state lifetimes and species concentrations, contributes to the rich and varied chemistry and dynamics found in diverse environments ranging from planetary atmospheres to the interstellar and circumstellar media. The nature and density of bound and resonance states, coupled electronic states, symmetry, and nuclear spin-statistics can all play a role. Here, we systematically investigate some of those factors by looking at the O 2 –Ar system, comparing rigorous quantum-scattering calculations for the 16 O 16 O– 40 Ar, 18 O 16 O– 40 Ar, and 18 O 18 O– 40 Ar isotope combinations. A new accurate potential energy surface was constructed for this purpose holding the O 2 bond distance at its vibrationally averaged distance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Collisional excitation of interstellar PN by H 2 : New interaction potential and scattering calculations

Here, rotational excitation of interstellar PN molecules induced by collisions with H 2 is investigated. We present the first ab initio four-dimensional potential energy surface (PES) for the PN–H 2 van der Waals system. The PES was obtained using an explicitly correlated coupled cluster approach with single, double, and perturbative triple excitations [CCSD(T)-F12b]. The method of interpolating moving least squares was used to construct an analytical PES from these data. The equilibrium structure of the complex was found to be linear, with H 2 aligned at the N end of the PN molecule, at an intermolecular separation of 4.2 Å. The corresponding well-depth is 224.3 cm -1 . The dissociation energies were found to be 40.19 cm -1 and 75.05 cm -1 for complexes of PN with ortho-H 2 and para-H 2 , respectively. Integral cross sections for rotational excitation in PN–H 2 collisions were calculated using the new PES and were found to be strongly dependent on the rotational level of the H 2 molecule. These new collisional data will be crucial to improve the estimation of PN abundance in the interstellar medium from observational spectra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

CF + excitation in the interstellar medium

The detection of CF + in interstellar clouds potentially allows astronomers to infer the elemental fluorine abundance and the ionization fraction in ultraviolet-illuminated molecular gas. Because local thermodynamic equilibrium (LTE) conditions are hardly fulfilled in the interstellar medium (ISM), the accurate determination of the CF + abundance requires one to model its non-LTE excitation via both radiative and collisional processes. Here, we report quantum calculations of rate coefficients for the rotational excitation of CF + in collisions with para- and ortho-H 2 (for temperatures up to 150 K). As an application, we present non-LTE excitation models that reveal population inversion in physical conditions typical of ISM photodissociation regions (PDRs). We successfully applied these models to fit the CF + emission lines previously observed toward the Orion Bar and Horsehead PDRs. The radiative transfer models achieved with these new rate coefficients allow the use of CF + as a powerful probe to study molecular clouds exposed to strong stellar radiation fields.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2020

Non-LTE modelling of cyanoacetylene: evidence for isomer-specific excitation

ABSTRACT Cyanoacetylene molecules are widespread in the interstellar medium (ISM) and several of its isomers have been detected in cold molecular clouds and circumstellar gas. Accurate estimates of the abundance ratio of cyanoacetylene isomers may provide deep insight into their environment. Such knowledge requires rigorous modelling of the emission spectra based on non-local thermodynamic equilibrium (LTE) radiative transfer calculations. To this end, we computed excitation cross-sections of HC2NC and HNC3 induced by collision with para- and ortho-H2, using a quantum mechanical close-coupling method. Then, by thermally averaging these data, we derived rate coefficients for the first 31 low-lying rotational levels of each isomer for temperatures up to 80 K. For the para-H2 collider, the propensity rules are in favour of rotational transitions involving Δj1 = 2 for both isomers, while for the ortho-H2 collider, Δj1 = 2 and Δj1 = 1 rotational transitions are favoured for HC2NC and HNC3, respectively. A comparison of rate coefficients for the HC3N isomers shows differences up to an order of magnitude, especially at low temperatures. Finally, we performed non-LTE radiative transfer calculations to assess the impact of such variations in the analysis of observations. Our simulation suggests that the lack of collisional data specific to each isomer could lead to errors up to a factor of 2–3 in the excitation temperatures. We expect that these data could help in better understanding the cyanoacetylene chemistry and constraining the nitrogen chemistry in the ISM.

79 ASTRONOMY AND ASTROPHYSICS↗