arXiv subjects

J. Loreau

Publications and source records attributed to J. Loreau.

At least 19 recordsLinked to original sources

arXiv2026

Aromatic rings in the Central Molecular Zone: Benzonitrile

In recent years, several aromatic molecules (benzene-based rings) have been detected in the cold molecular cloud TMC-1, with its CN-derivative, benzonitrile (c-C$_6$H$_5$CN), also identified in other nearby cold sources. However, observed abundances differ significantly from chemical model predictions, indicating an incomplete understanding of its chemistry and motivating searches in distinct environments. We report new detections of benzonitrile in two warmer molecular clouds of the Central Molecular Zone (CMZ): G+0.693-0.027 and G+0.633-0.0604. Using Yebes 40m ultra-deep surveys in the 31--50 GHz range, we performed LTE and non-LTE analyses to derive the physical parameters of the emission. We obtain column densities of $N$=(7.4$\pm$0.5)$\times10^{12}$ and (2.60$\pm$0.13)$\times10^{12}$ cm$^{-2}$, corresponding to abundances relative to H$_2$ of (6$\pm$1)$\times10^{-11}$ and (4.3$\pm$0.9)$\times10^{-11}$, consistent with values in cold Galactic clouds. The HC$_7$N/benzonitrile ratio is lower (2.15-2.4) than in colder sources (4.5-30), suggesting environmental effects and a relative enhancement of aromatic chemistry in the CMZ. These results confirm that benzonitrile is widespread and can survive in harsher environments (e.g., high temperatures, shocks, enhanced cosmic-ray ionization) than those in Galactic cold clouds. This suggests that aromatics are stable and abundant species that can significantly contribute to the total budget of interstellar carbon in molecular clouds. A top-down formation scenario, involving fragmentation of larger carbonaceous species, is consistent with the nearly constant abundances observed with molecular size.

astro-ph.GA↗

arXiv2024

Collisional excitation of propyne (CH$_3$CCH) by He atoms

A detailed interpretation of the detected emission lines of environments in which propyne (or methyl acetylene, CH$_3$CCH) is observed requires a knowledge of its collisional rate coefficients with the most abundant species in the interstellar medium, He or H$_2$. We present the first three-dimensional potential energy surface (3D-PES) for the CH$_3$CCH-He molecular complex, study the dynamics of the collision, and report the first set of rate coefficients for temperatures up to 100 K for the collisional excitation of the lowest 60 ortho rotational levels and 60 para rotational levels of CH$_3$CCH by He atoms. We computed the 3D-PES with the explicitly correlated coupled-cluster with single-, double-, and perturbative triple-excitation method, in conjunction with the augmented correlation-consistent triple zeta basis set (CCSD(T)-F12a/aug-cc-pVTZ). The 3D-PES was fitted to an analytical function. Scattering computations of pure rotational (de-)excitation of CH$_3$CCH by collision with He atoms were performed and the state-to-state cross sections were computed using the close coupling method for total energies up to 100 cm$^{-1}$ and with the coupled states approximation at higher energy for both ortho and para symmetries of CH$_3$CCH. The PES obtained is caracterized by a large anisotropy and a potential well depth of 51.04 cm$^{-1}$. By thermally averaging the collisional cross sections, we determined quenching rate coefficients for kinetic temperatures up to 100 K. A strong even $Δj$ propensity rule at almost all collision energies exists for CH$_3$CCH-He complex. To evaluate the impact of rate coefficients in the analysis of observations, we carried out non-LTE radiative transfer computations of the excitation temperatures and we demonstrate that LTE conditions are typically not fulfilled for the propyne molecule.

astro-ph.GA↗

arXiv2024

Rotational excitation of interstellar benzonitrile by helium atoms

Interstellar aromatic molecules such as polycyclic aromatic hydrocarbons and polycyclic nitrogen and oxygen bearing molecules are thought to be abundant in the interstellar medium. In this class of molecules, benzonitrile ($c$-C$_6$H$_5$CN) plays an important role as a proxy for benzene. It has been detected through rotational emission in several astrophysical sources and is one of the simplest N-bearing polar aromatic molecules. Even in the cold ISM, the population of the rotational levels of benzonitrile might not be at equilibrium. Consequently, modeling its detected emission lines requires a prior computation of its quenching rate coefficients by the most abundant species in the ISM (He or H$_2$). In this paper, we focus on the excitation of c-C$_6$H$_5$CN by collision with He. We compute the first potential energy surface (PES) using the explicitly correlated coupled cluster method in conjunction with large basis sets. The PES obtained is characterized by a potential well depth of -97.2 cm$^{-1}$ and an important anisotropy. Scattering computations of the rotational (de-)excitation of c-C$_6$H$_5$CN by He atoms are performed by means of the coupled states approximation that allow to obtain collisional rates for rotational states up to $j$ = 9 and temperatures up to 40 K. These rate coefficients are then used to examine the effect of C$_6$H$_5$CN excitation induced by collisions with para-H$_2$ in molecular clouds by carrying out simple radiative transfer calculations of the excitation temperatures and show that non-equilibrium effects can be expected for H$_2$ densities up to 10$^5$-10$^6$ cm$^{-3}$.

astro-ph.GA↗

arXiv2023

Collisional excitation of methyl (iso)cyanide by He atoms: rate coefficients and isomerism effects

Among all closed-shell species observed in molecular clouds, molecules with C$_{3v}$ symmetry play a crucial role, as their rotational spectroscopy allows them to behave as a gas thermometer. In the interstellar medium, methyl cyanide (CH$_3$CN) is the second most abundant of those (after ammonia, NH$_3$). Its isomer, methyl isocyanide (CH$_3$NC) is less abundant but has been detected in many astrophysical sources. In order to assess their absolute and relative abundances, it is essential to understand their collisional excitation properties. This paper reports the calculation of rate coefficients for rotational excitation of CH$_3$CN and CH$_3$NC molecules with He atoms, from low (5 K) to moderate (100 K) temperatures. We include the first 74 and 66 rotational states of both $para$ and $ortho$ symmetries of CH$_3$CN and CH$_3$NC, respectively. A propensity for $Δj=2$ transitions is observed in the case of CH$_3$CN-He collisions, whereas in the case of CH$_3$NC-He a propensity for $Δj=1$ is observed for transitions involving low values of $j$ and at low temperatures, while a propensity for $Δj=2$ is observed for higher values of $j$ and at high temperatures. A comparison of rate coefficients shows differences up to a factor of 3, depending on temperature and on the $ortho$/$para$ symmetries for dominant transitions. This confirms the importance of having specific collisional data for each isomer. We also examined the effect of these new rates on the CH$_3$CN and CH$_3$NC excitation in molecular clouds by performing radiative transfer calculations of the excitation and brightness temperatures for several detected lines.

astro-ph.GA↗

arXiv2023

Hyperfine collisional excitation of ammonia by molecular hydrogen

Ammonia is one of the most widely observed molecules in space, and many observations are able to resolve the hyperfine structure due to the electric quadrupole moment of the nitrogen nucleus. The observed spectra often display anomalies in the satellite components of the lines, which indicate substantial deviations from the local thermodynamic equilibrium. The interpretation of the spectra thus requires the knowledge of the rate coefficients for the hyperfine excitation of NH$_3$ induced by collisions with H$_2$ molecules, the dominant collider in the cold interstellar medium. In this paper we present the first such calculations using a recoupling approach. The rate coefficients are obtained for all hyperfine levels within rotation-inversion levels up to $j=4$ and temperatures up to 100 K by means of quantum scattering close-coupling calculations on an accurate, five-dimensional, potential energy surface. We show that the rate coefficients depart significantly from those obtained with the statistical approach and that they do not conform to any simple propensity rules. Finally, we perform radiative transfer calculations to illustrate the impact of our new rate coefficients by modelling the hyperfine line intensities of the inversion transition in ground state para-NH$_3$ ($j_k=1_1$) and of the rotational transition $1_0\rightarrow 0_0$ in ortho-NH$_3$.

astro-ph.GA↗

arXiv2022

The effect of water and electron collisions in the rotational excitation of HF in comets

We present the first set of rate coefficients for the rotational excitation of the 7 lowest levels of hydrogen fluoride (HF) induced by collision with water molecules, the dominant collider in cometary comas, in the 5-150 K temperature range. The calculations are performed with a quantum statistical approach from an accurate rigid rotor ab initio interaction potential. Rate coefficients for excitation of HF by electron-impact are also computed, within the Born approximation, in the 10-10,000 K temperature range. These rate coefficients are then used in a simplified non-local thermodynamic equilibrium (non-LTE) model of a cometary coma that also includes solar radiative pumping and radiative decay. We investigate the range of H2O densities that lead to non-LTE populations of the rotational levels of HF. We show that to describe the excitation of HF in comets, considering collisions with both water molecules and electrons is needed as a result of the large dipole of HF.

astro-ph.EP↗

arXiv2022

Fine and hyperfine excitation of nitric oxide by collision with para-H2

Nitric oxide is an open-shell molecule abundantly detected in the interstellar medium. A precise modeling of its radiative and collisional processes opens the path to a precise estimate of its abundance. We present here the first rate coefficients for fine and hyperfine (de-)excitation of NO by collisions with the most ubiquitous collision partner in the interstellar medium, $para$-H$_2$ hydrogen molecules, using a recently developed accurate interaction potential. We report quantum scattering calculations for transitions involving the first 74 fine levels and the corresponding 442 hyperfine levels belonging to both $F_1$ and $F_2$ spin-orbit manifolds. To do so, we have calculated cross sections by means of the quantum mechanical close-coupling approach up to 1000 cm$^{-1}$ of total energy and rate coefficients from 5 to 100 K. Propensity rules are discussed and the new NO-H$_2$ rates are compared to those available in the literature, based on scaled NO-He rates. Large differences are observed between the two sets of rate coefficients, and this comparison shows that the new collision rates must be used in interpreting NO emission lines. We also examined the effect of these new rates on the NO excitation in cold clouds by performing radiative transfer calculations of the excitation and brightness temperatures for the two NO lines at 150.176 and 250.4368 GHz. This shows that the local thermodynamic equilibrium is not fulfilled for this species for typical conditions. We expect the use of the rates presented in this study to improve the constraints on the abundance of NO.

astro-ph.GA↗

arXiv2020

Cold collisions of C$_{2}^{-}$ anions with Li and Rb atoms in hybrid traps

We present a theoretical investigation of reactive and non-reactive collisions of Li and Rb atoms with C$_{2}^{-}$ molecular anions at low temperatures in the context of sympathetic cooling in hybrid trap experiments. Based on recently reported accurate potential energy surfaces for the singlet and triplet states of the Li-C$_{2}^{-}$ and Rb-C$_{2}^{-}$ systems, we show that the associative electronic detachment reaction is slow if the colliding partners are in their ground state, but fast if they are excited. The results are expected to be representative of the alkali-metal series. We also investigate rotationally inelastic collisions in order to explore the cooling of the translational and rotational degrees of freedom of C$_2^-$ in hybrid ion-atom traps. The effect of micromotion is taken into account by considering Tsallis distributions of collision energies. We show that the translational cooling occurs much more rapidly than rotational cooling and that the presence of excited atoms leads to losses of anions on a timescale comparable to that of rotational cooling.

physics.chem-ph↗

arXiv2020

The effect of CO-H2O collisions in the rotational excitation of cometary CO

We present the first accurate rate coefficients for the rotational excitation of CO by H2O in the kinetic temperature range 5-100 K. The statistical adiabatic channel method (SACM) is combined with a high-level rigid-rotor CO-H2O intermolecular potential surface. Transitions among the first 11 rotational levels of CO and the first 8 rotational levels of both para-H2O and ortho-H2O are considered. Our rate coefficients are compared to previous data from the literature and they are also incorporated in a simple non-LTE model of cometary coma including collision-induced transitions, solar radiative pumping and radiative decay. We find that the uncertainties in the collision data have significant influence on the CO population distribution for H2O densities in the range 10^3-10^8 cm^-3. We also show that the rotational distribution of H2O plays an important role in CO excitation (owing to correlated energy transfer in both CO and H2O), while the impact of the ortho-to-para ratio of H2O is found to be negligible.

astro-ph.EP↗

arXiv2019

Photodissociation as a probe of the H$_3^+$ avoided crossing seam

Experiments are conducted to investigate the role of the avoided crossing seam in the photodissociation of H$_3^+$. Three-dimensional imaging of dissociation products is used to determine the kinetic energy release and branching ratio among the fragmentation channels. Vibrational distributions are measured by dissociative charge transfer of H$_2^+$ products. It is found that the photodissociation of hot H$_3^+$ in the near ultraviolet produces cold H$_2^+$, but hot H$_2$. Modelling the wavepacket dynamics along the repulsive potential energy surface accounts for the repopulation of the ground potential energy surface. The role of the avoided crossing seam is emphasized and its importance for the astrophysically relevant charge transfer reactions is underlined.

physics.chem-ph↗

arXiv2018

Charge transfer in H + He$^+$ and H$^+$ + He collisions in excited states

We present a theoretical study of charge transfer in collisions of excited ($n=2,3$) hydrogen atoms with He$^+$ and in collisions of excited ($n=2,3$) helium atoms with H$^+$, extending the results of Phys. Rev. A 82 012708 (2010). A combination of quantum-mechanical and semi-classical approaches is employed to calculate the charge-exchange cross sections at collision energies from 0.1 eV/u up to 1 keV/u. These methods are based on accurate ab initio potential energy curves and non-adiabatic couplings for the molecular ion HeH$^+$. Charge transfer can occur either in singlet or in triplet states, and the differences between the singlet and triplet spin manifolds are discussed. The dependence of the cross section on the quantum numbers $n$ and $l$ of the initial state is demonstrated. The isotope effect on the charge transfer cross sections, arising at low collision energy when H is substituted by D or T, is investigated. Finally, the impact of the present calculations on models of laboratory plasmas is discussed.

physics.atom-ph↗

arXiv2015

Simulating rotationally inelastic collisions using a Direct Simulation Monte Carlo method

A new approach to simulating rotational cooling using a direct simulation Monte Carlo (DSMC) method is described and applied to the rotational cooling of ammonia seeded into a helium supersonic jet. The method makes use of ab initio rotational state changing cross sections calculated as a function of collision energy. Each particle in the DSMC simulations is labelled with a vector of rotational populations that evolves with time. Transfer of energy into translation is calculated from the mean energy transfer for this population at the specified collision energy. The simulations are compared with a continuum model for the on-axis density, temperature and velocity; rotational temperature as a function of distance from the nozzle is in accord with expectations from experimental measurements. The method could be applied to other types of gas mixture dynamics under non-uniform conditions, such as buffer gas cooling of NH$_3$ by He.

physics.chem-ph↗

arXiv2013

Determination of photodissociation and radiative association cross sections from the same time-dependent calculation

We illustrate some of the difficulties that may be encountered when computing photodissociation and radiative association cross sections from the same time-dependent approach based on wavepacket propagation. The total and partial photodissociation cross sections from the thirty-three vibrational levels of the b triplet Σ+ state of HeH+ towards the 9 other triplet Σ+ and 6 triplet Π n = 2, 3 higher-lying electronic states are calculated. The corresponding radiative association cross sections are extracted from the same calculations, and the photodissociation and radiative association rate constants are determined.

physics.chem-ph↗

arXiv2013

Potential energy curves for the interaction of Ag(5s) and Ag(5p) with noble gas atoms

We investigate the interaction of ground and excited states of a silver atom with noble gases (NG), including helium. Born-Oppenheimer potential energy curves are calculated with quantum chemistry methods and spin-orbit effects in the excited states are included by assuming a spin-orbit splitting independent of the internuclear distance. We compare our results with experimentally available spectroscopic data, as well as with previous calculations. Because of strong spin-orbit interactions, excited Ag-NG potential energy curves cannot be fitted to Morse-like potentials. We find that the labeling of the observed vibrational levels has to be shifted by one unit.

physics.chem-ph↗

arXiv2013

Photodissociation and radiative association of HeH+ in the metastable triplet state

We investigate the photodissociation of the metastable triplet state of HeH+ as well as its formation through the inverse process, radiative association. In models of astrophysical plasmas, HeH+ is assumed to be present only in the ground state, and the influence of the triplet state has not been explored. It may be formed by radiative association during collisions between a proton and metastable helium, which are present in significant concentrations in nebulae. The triplet state can also be formed by association of He+ and H, although this process is less likely to occur. We compute the cross sections and rate coefficients corresponding to the photodissociation of the triplet state by UV photons from a central star using a wave packet method. We show that the photodissociation cross sections depend strongly on the initial vibrational state and that the effects of excited electronic states and non-adiabatic couplings cannot be neglected. We then calculate the cross section and rate coefficient for the radiative association of HeH+ in the metastable triplet state.

physics.chem-ph↗

arXiv2013

Index of refraction of molecular nitrogen for sodium matter waves

We calculate the index of refraction of sodium matter waves propagating through a gas of nitrogen molecules. We use a recent ab initio potential for the ground state of the NaN_2 Van der Waals complex to perform quantal close-coupling calculations and compute the index of refraction as a function of the projectile velocity. We obtain good agreement with the available experimental data. We show that the refractive index contains glory oscillations, but that they are damped by the averaging over the thermal motion of the N_2 molecules. These oscillations appear at lower temperatures and projectile velocity. We also investigate the behavior of the refractive index at low temperature and low projectile velocity to show its dependence on the rotational state of N_2, and discuss the advantage of using diatomic molecules as projectiles.

physics.atom-ph↗

arXiv2011

Ro-vibrational analysis of the XUV photodissociation of HeH$^+$ ions

We investigate the dynamics of the photodissociation of the hydrohelium cation HeH$^+$ by XUV radiation with the aim to establish a detailed comparison with a recent experimental work carried out at the FLASH free electron laser using both vibrationally hot and cold ions. As shown in previous theoretical works, the comparison is hindered by the fact that the experimental ro-vibrational distribution of the ions is unknown. We determine this distribution using a dissociative charge transfer set-up and the same source conditions as in the FLASH experiment. Using a non-adiabatic time-dependent wave packet method, we calculate the partial photodissociation cross sections for the $n=1-3$ coupled electronic states of HeH$^+$. We find a good agreement with the experiment for the total cross section into the He + H$^+$ dissociative channel. By performing an adiabatic calculation involving the $n=4$ states, we then show that the experimental observation of the importance of the electronic states with $n>3$ cannot be well explained theoretically, especially for cold ($v=0$) ions. We also calculate the relative contributions to the cross section of the $Σ$ and $Π$ states. The agreement with the experiment is excellent for the He$^+$ + H channel, but only qualitative for the He + H$^+$ channel. We discuss the factors that could explain the remaining discrepancies between theory and experiment.

physics.atom-ph↗

arXiv2010

Radiative lifetime of the $a\ ^3Σ^+$ state of HeH$^+$ from ab initio calculations

The first metastable triplet state of HeH$^+$ was found to be present in ion beam experiments, with its lifetime estimated to be between hundreds of milliseconds and thousand of seconds. In this work, we use {\it ab initio} methods to evaluate the radiative lifetimes of the six vibrational levels of the $a\ ^3Σ^+$ of HeH$^+$. The transition $a\ ^3Σ^+ \rightarrow X \ ^1Σ^+$ is spin-forbidden, but acquires intensity through spin-orbit interaction with the singlet and triplet $Π$ states. Large scale CASSCF/MRCI calculations using an adapted basis set were performed to determine the potential energy curves of the relevant states of HeH$^+$ as well as the matrix elements of the dipole and spin-orbit operators. The wave functions and energies of the vibrational levels of the $a\ ^3Σ^+$ and $X \ ^1Σ^+$ states are obtained using a B-spline method and compared to previous works. We find that radiative lifetime of the vibrational levels increases strongly with $v$, the lifetime of the $v=0$ state being of 150 s. We also analyze the contributions from discrete and continuum parts of the spectrum. With such a long lifetime, the $a\ ^3Σ^+$ state could have astrophysical implications.

physics.atom-ph↗