arXiv subjects

François Lique

Publications and source records attributed to François Lique.

At least 19 recordsLinked to original sources

arXiv2026

Interactions and dynamics of metastable triplet-state helium dimer with Ne and Ar

Helium dimer in its metastable triplet electronic state, He$_2(a~^3Σ_u^+)$, is a promising candidate for direct laser cooling and precision measurements. Interactions and collisions involving He$_2(a~^3Σ_u^+)$ remain unexplored in ultracold and cold energy domains. Here, we present the first theoretical investigation of intermolecular interactions and collision dynamics of He$_2(a~^3Σ_u^+)$+Ne van der Waals complex. For the ground electronic state, $X~^3\mathrm{A}'$, we employ a spin-restricted coupled cluster method with single, double, and noniterative triple excitations. The resulting interaction potential exhibits an extremely shallow well with a depth of 4.612 cm$^{-1}$. We construct a three-dimensional vibrationally averaged potential energy surface. Using this surface, we perform full close-coupling calculations including fine-structure levels of He$_2(a~^3Σ_u^+)$ to investigate collisional excitation and quenching induced by Ne. We analyze the low-energy scattering dynamics and model resonant features associated with quasi-bound states supported by interaction potential. Propensity rule for fine-structure conserving transitions is established. We additionally consider He$_2$+Ar collisions and compare their energy dependence and resonance structure with those of He$_2$+Ne. The He$_2$+Ar system exhibits a richer resonance structure, highlighting the sensitivity of low-energy scattering to interaction potential and reduced mass. Calculated PES and scattering properties provide a reliable benchmark for description of He$_2$+Ne van der Waals complex and may be useful for interpretation of future experimental spectra and collision measurements.

physics.atom-ph↗

arXiv2026

Collisional excitation of E- and Z-ethanimine to model cold molecular clouds

Context. Ethanimine is a prebiotically relevant complex organic molecule that has been proposed as a key precursor of amino acids in the interstellar medium. To date, both its E and Z isomers have only been detected toward the Sgr B2(N) molecular cloud. The pronounced non-local thermodynamic equilibrium (non-LTE) effects predicted for this molecule require accurate collisional rate coefficients for reliable astrophysical modeling and future astronomical searches. Aims. We aim to provide the first collisional datasets for both ethanimine isomers with the main cold molecular clouds collision partners, He and para-H2, in order to support non-LTE radiative-transfer modeling. Methods. State-to-state rate coefficients for collisions with He were computed by integration over mixed close-coupling (CC) and coupled-states (CS) scattering cross sections at different energy ranges. In addition, comparisons with mixed quantum-classical theory (MQCT) calculations performed for both He and para-H2 collisions enabled the derivation of transition-specific scaling factors, which were applied to predict collisional rate coefficients for para-H2. Results. We present the first state-to-state collisional datasets for both E- and Z-ethanimine in collision with He and para-H2, including all rotational transitions involving levels below 50 cm-1 and over the 5-100 K temperature range. Conclusions. The datasets reported here provide the first collisional information suitable for non-LTE modeling of ethanimine in cold interstellar environments. They represent a key step toward more reliable abundance determinations and may facilitate future astronomical detections of both ethanimine isomers beyond Sgr B2(N).

astro-ph.GA↗

arXiv2026

Collisional excitation of cyclopentadiene by helium. A complete set of rate coefficients and astrophysical applications

Complex organic molecules, including large cyclic species, are prevalent in interstellar space and play a key role in various astrochemical processes. Cyclopentadiene (c-C5H6) is a five-membered cyclic hydrocarbon recently detected in TMC-1 and some other interstellar molecular clouds. While accurate spectroscopic data were available, collisional rate coefficients for its rotational transitions were missing so far, introducing a potential limitation in the interpretation of the observations. This study aims to provide a comprehensive set of state-to-state thermal rate coefficients for the rotational excitation of c-C5H6 due to collisions with helium, crucial for non-local thermodynamic equilibrium (non-LTE) radiative transfer modelling in astrophysical environments, and to examine how far the molecule is from thermalisation under the physical conditions of cold molecular clouds. The research employed accurate quantum scattering calculations using the close-coupling (CC) and coupled states (CS) methods, based on a highly-correlated three-dimensional potential energy surface for the [c-C5H6 + He] collisional complex. Calculations were performed for a wide range of rotational states (from j = 0 to j \leq 25) and kinetic temperatures (from 10 to 50 K). We calculated a complete set of thermal rate coefficients for both ortho- and para-C5H6. Radiative transfer simulations demonstrated that most rotational levels of cyclopentadiene are fully thermalized under typical cold cloud conditions and exhibit minor non-LTE effects. Nevertheless, this study is the first to utilise accurate state-to-state rate coefficients for radiative transfer simulation of a large, five-membered cyclic species detected in space. This allows to draw some general conclusions and paves the way for future studies of complex astromolecules that will enable a more precise interpretation of upcoming detections.

astro-ph.GA↗

arXiv2026

Isomer-specific excitation of formic acid in collisions with helium atoms

An accurate estimation of the molecular abundances of isomers in the interstellar medium (ISM) is necessary to unravel the underlying chemistry and physics. After the recent detections of both isomers of formic acid ($cis-$ and $trans-$HCOOH) in dense dark cold clouds, their accurate molecular line modeling became of interest. The conditions of these environments do not necessarily follow the local thermodynamic equilibrium, thus taking into account the competition between the radiative and collisional processes is required. This involves the knowledge of the rotational excitation data for collisions with the most abundant interstellar species \textemdash He and H$_2$. In this paper, the first potential energy surfaces (PES) for the interaction of the two rotamers of formic acid with He atoms are computed using the explicitly correlated coupled-cluster theory [CCSD(T)-F12]. The obtained PESs demonstrate qualitative similarities and high anisotropy. The global minima are found with $V=-53.0$ cm$^{-1}$ and $V=-46.0$ cm$^{-1}$ for $cis-$HCOOH and $trans-$HCOOH respectively. Collisional excitation cross sections calculated for total energies up to 100 cm$^{-1}$ demonstrate similar propensity rules for both isomers. Quantitative differences of the cross sections associated with the two rotamers are also discussed.

astro-ph.GA↗

arXiv2026

Collisional energy transfer in ethanimine + He system

The ethanimine molecule, CH3CHNH, is one of the prebiotic molecules detected by astronomers in chemically-rich molecular clouds in the Galactic Center. The observations indicate a non-equilibrium distribution of rotational state populations in both the E- and Z-isomers of ethanimine, resulting from the competition between radiative processes and collisions with background gases such as He and H2. Accurate interpretation of these observations requires the use of radiative transfer models with collisional state-to-state transition processes included. Here, in order to compute cross sections for state-to-state transitions in both ethanimine isomers, accurate potential energy surfaces for their interaction with a He atom were constructed and three complementary methods for inelastic scattering were utilized: full-quantum coupled-channel and coupled-states methods, and the mixed quantum/classical theory. Strong propensities of transitions toward $Δj = 0$ and either $Δk_a = 0$ (with $Δk_c = \pm 1$) or $Δk_c = 0$ (with $Δk_a = \pm 1$) are reported and the origin of this effect is identified. Small but non-negligible differences between energy transfer in the two isomers, on the order of 10%, were found. The utility of the mixed quantum/classical approach to collisional energy transfer at higher collision energies is discussed.

physics.chem-ph↗

arXiv2026

Quantum and Structural Effects Captured via a Statistical Method: the SACM Applied to HCN and HNC Colliding with CO

This work spotlights the Statistical Adiabatic Channel Model as an efficient and accurate method for deriving low temperature (de)-excitation rate coefficients for collisions induced by heavy projectiles. For such systems, fully quantum treatments become intractable, while quasi-classical methods fail at low temperature. Here, we demonstrate that the Statistical Adiabatic Channel Model overcomes these limitations by combining statistical sampling with an adiabatic channel representation. Its application to the HCN and HNC isomers colliding with CO yields rate coefficients in quantitative agreement with full quantum results benchmarked for the lowest total angular momentum. These systems are relevant for modeling cometary comae, where reliable molecular data remain scarce. Remarkably, this approach also reproduces near-resonant energy transfer and isomeric effects, demonstrating that essential quantum and structural features can be captured within a statistical framework.

astro-ph.GA↗

arXiv2026

Chemistry and ro-vibrational excitation of CH$^+$ in the planetary nebula NGC 7027

Small carbon hydride cations, such as the methylidyne ion (CH$^+$), play an important role in the chemistry of the interstellar medium (ISM). They participate in gas-phase reaction networks leading to the formation of hydrocarbon species that act as precursors to more complex organic molecules. CH$^+$ is a highly reactive ion that is rapidly destroyed by H, H$_2$, and free electrons, making its excitation challenging to model. Its level populations depend not only on radiative and inelastic processes but also on chemical formation and destruction rates, a mechanism known as chemical pumping. We investigate this effect using a new set of ab initio state-resolved ro-vibrational (reactive and inelastic) collision data to model the observed CH$^+$ emission. Multiple rotational and ro-vibrational transitions of CH$^+$ detected toward the planetary nebula NGC 7027 are analyzed. The chemical structure of CH$^+$ is modeled with the CLOUDY code using updated reaction rates, providing the temperature and density structure across the nebula. A non-local thermodynamic equilibrium (NLTE) analysis is performed using CLOUDY and the single-zone RADEX code with a comprehensive set of spectroscopic and collisional data. In addition, chemical formation and destruction processes are implemented in RADEX and explored via Markov Chain Monte Carlo sampling. The CLOUDY model reproduces the observed CH$^+$ line fluxes within a factor of 1.3 on average. It indicates that rotational and ro-vibrational lines arise from physically distinct regions, primarily differing in temperature. RADEX models show that chemical pumping significantly enhances populations above ($\upsilon = 0, J = 1$), strongly increasing ro-vibrational emission, especially in the $\upsilon =2 \to 1$ band. Single-zone models remain limited, highlighting the need for full 1D modeling including all excitation processes.

astro-ph.GA↗

arXiv2025

Collisional excitation of HCN by CO to refine the modeling of cometary comae

We present the first dataset of collisional (de)-excitation rate coefficients of HCN induced by CO, one of the main perturbing gases in cometary atmospheres. The dataset spans the temperature range of 5-50 K. It includes both state-to-state rate coefficients involving the lowest ten and nine rotational levels of HCN and CO, respectively, and the so-called "thermalized" rate coefficients over the rotational population of CO at each kinetic temperature. The derivation of these coefficients exploited the good performance of the statistical adiabatic channel model (SACM) on top of an accurate interaction potential computed at the CCSD(T)-F12b/CBS level of theory. The reliability of the SACM approach was validated by comparison with full quantum calculations restricted at the lowest total angular momentum of the system. These results provide essential input to accurately model the distribution among the rotational energy levels and the abundance of HCN in cometary atmospheres, accounting for deviations from local thermodynamic equilibrium that typically occurs in such environments.

astro-ph.EP↗

arXiv2025

Experimental and theoretical investigation on N2 pressure-induced coefficients of the lowest rotational transitions of HCN

We present the first experimental determination of room-temperature N2 pressure broadening, speed dependent broadening, and pressure shift coefficients of the three lowest rotational lines of HCN. The experimental results served to assess the accuracy of a low-cost yet accurate computational strategy, which relies on a simplified characterization of the HCN-N2 interaction potential, and employs a novel approximate method of solving the quantum scattering problem. Building on the validation of this computational approach, the dataset was extended to higher rotational transitions, up to J(HCN)=5-4. For these transitions, we provide the temperature dependence of the pressure broadening coefficient, its speed dependence parameter, and the Dicke narrowing parameter. This new dataset can support and refine the modeling of HCN in both the terrestrial and Titan's atmospheres. This work constitutes an important step towards populating spectroscopic databases with accurate HCN line-shape parameters.

physics.chem-ph↗

arXiv2025

An 18-25 GHz spectroscopic survey of dense cores in the Chamaeleon I molecular cloud

We extend the survey for organics in the southern hemisphere by observing two cores in the Chamaeleon complex using NASA's Deep Space Network 70-m antenna in Canberra, Australia, over the frequency range of 18 to 25 GHz. We surveyed the class 0 protostar Cha-MMS1 and the prestellar core Cha-C2, which represent two stages in the evolution of dense cores. We detect several molecules including HC$_3$N, HC$_5$N, C$_4$H, CCS, C$_3$S, NH$_3$, and c-C$_3$H$_2$. A longer cyanopolyyne, HC$_7$N, is detected with high confidence via spectral stacking analysis. While molecular column densities in the two Chamaeleon cores are typically an order of magnitude lower compared to the cynaopolyyne peak in TMC-1, the molecular abundance ratios are in general agreement with the TMC-1 values. The two exceptions are c-C$_3$H$_2$, which is enhanced by a factor of \about 25 with respect to cyanopolyynes in the Chamaeleon cores, and ammonia, which is enhanced by a factor of ~ 125. The deuterated species c-C$_3$HD is detected in both cores, with a high D/H ratio of ~0.23 in c-C$_3$H$_2$. A rare isotopologue of ammonia, $^{15}$NH$_3$, is also detected in Cha-MMS1 suggesting a high $^{14}$N/$^{15}$N ratio of ~ 690 in ammonia. However, this ratio may be artificially enhanced due to the high optical depth of the $^{14}$NH$_3$ (1,1) line, which increases the effective source size. We use the detections of ammonia, cyanopolyynes, and far-infrared dust continuum to characterize the density and temperature in the Chamaeleon cores and calculate the molecular column densities and their relative ratios. The ring molecule benzonitrile is not detected in either Chamaeleon core. The $3 σ$ upper limits for its column density are a factor of 2 higher than the value derived for TMC-1 and the upper limits for its relative abundance with respect to HC$_5$N are a factor of 3 higher than the TMC-1 value.

astro-ph.GA↗

arXiv2025

Chemistry and ro-vibrational excitation of HeH$^+$ in the Planetary Nebula NGC 7027

HeH$^+$ belongs to the class of "reactive" ions that can be destroyed so quickly that chemical formation and destruction rates may compete with inelastic rates and should be considered when solving the statistical equilibrium equations. This so-called chemical "pumping" or "excitation" effect is investigated here for the first time in HeH$^+$. The chemical evolution of HeH$^+$ in NGC 7027 is modeled with the CLOUDY photoionization code using updated reaction rate coefficients. The non-LTE analysis of the three observed HeH$^+$ emission lines is then performed with the CLOUDY and RADEX codes using an extensive set of spectroscopic and inelastic collisional data suitable for the specific high-temperature environment of NGC 7027. In a second approach, chemical formation and destruction rates of HeH$^+$ are implemented in RADEX. This code is combined with MCMC sampling (performed on the RADEX-parameters space) to extract the best-fit HeH$^+$ column density and physical conditions from the observed line fluxes. The CLOUDY and RADEX non-LTE results are found to be in good agreement, and the $\upsilon=1-0 \ P(2)/P(1)$ line ratio is better than 20%. Agreement to better than a factor of 2.3 is obtained when including the reaction between He($2^3S$) and H as an additional source of HeH$^+$. The RADEX/MCMC model with chemical pumping is found to reproduce both the observed line fluxes and the line ratio to 20%. Our results suggest that additional HeH$^+$ lines must be detected in NGC 7027 to better constrain the physical conditions via non-LTE models. Uncertainties in collisional (reactive and inelastic) data of HeH$^+$ have been largely reduced in this work. The three observed lines are not sensitive to chemical pumping while excited "short-lived" levels are significantly overpopulated with respect to a non-LTE model neglecting chemical excitation.

astro-ph.GA↗

arXiv2024

Rotational excitation cross sections for chloronium based on a new 5D interaction potential with molecular hydrogen

Chloronium (H$_2$Cl$^+$) is an important intermediate of Cl-chemistry in space. The accurate knowledge of its collisional properties allows a better interpretation of the corresponding observations in interstellar clouds and therefore a better estimation of its abundance in these environments. While the ro-vibrational spectroscopy of H$_2$Cl$^+$ is well known, the studies of its collisional excitation are rather limited and these are available for the interaction with helium atoms only. We provide a new 5-dimensional rigid-rotor potential energy surface for the interaction of H$_2$Cl$^+$ with H$_2$, calculated from explicitly correlated coupled cluster ab initio theory, which was fitted then with a set of analytical functions, allowing to perform scattering calculations using accurate quantum theories. We analyze the collision-energy-dependence of the rotational state-to-state cross sections and the temperature dependence of the corresponding thermal rate coefficients, with a particular attention on the collisional propensity rules. When comparing our results for collisions with H$_2$ with those obtained with He as a colliding partner, we found very significant differences with non-linear scaling trends, which proves again that He is not a suitable proxy for collisions between hydride molecules and molecular hydrogen, the most abundant gas particle in the interstellar medium.

physics.chem-ph↗

arXiv2024

Fate and detectability of rare gas hydride ions in nova ejecta: A case study with nova templates

HeH$^+$ was the first heteronuclear molecule to form in the metal-free Universe after the Big Bang. The molecule gained significant attention following its first circumstellar detection in the young and dense planetary nebula NGC 7027. We target some hydride ions associated with the noble gases (HeH$^+$, ArH$^+$, and NeH$^+$) to investigate their formation in harsh environments like the nova outburst region. We use a photoionization modeling (based on previously published best-fit physical parameters) of the moderately fast ONe type nova, QU Vulpeculae 1984, and the CO type novae, RS Ophiuchi and V1716 Scorpii. Our steady-state modeling reveals a convincing amount of HeH$^+$, especially in the dense clump of RS Ophiuchi and V1716 Scorpii. The calculated upper limit on the surface brightness of HeH$^+$ transitions suggests that the James Webb Space Telescope (JWST) could detect some of them, particularly in sources like RS Ophiuchi and V1716 Scorpii, which have similar physical and chemical conditions and evolution. It must be clearly noted that the sources studied are used as templates, and not as targets for observations. The detection of these lines could be useful for determining the physical conditions in similar types of systems and for validating our predictions based on new electron-impact ro-vibrational collisional data at temperatures of up to 20,000 K.

astro-ph.GA↗

arXiv2024

First close-coupling study of the excitation of a large cyclic molecule: collision of c-C5H6 with He

Recent astronomical observations revealed an increasing molecular complexity in the interstellar medium through the detection of a series of large cyclic carbon species. To correctly interpret these detections, a complex analysis is necessary that takes into account the non-local thermodynamic equilibrium (non-LTE) conditions of the emitting media (e.g. when energy level populations deviate from a Boltzman distribution). This requires proper state-to-state collisional data for the excitation and de-excitation processes of the molecular levels. Cyclopentadiene (c-C5H6), which was recently detected in multiple cold interstellar clouds, is extensively studied in many aspects due to its large importance for chemistry in general. At the same time, there are no collisional data available for this species, which are necessary for a more precise interpretation of the corresponding detections. In this work, we first provide an accurate 3D rigid-rotor interaction potential for the [c-C5H6 + He] complex from high-level of ab initio theories, which has been used to study their inelastic collision by the exact close coupling quantum scattering method. To the best of our knowledge, this is the first study where this method is systematically applied to treat the dynamics of molecular collisions involving more than ten atoms. We also analyse the collisional propensity rules and the differences in contrast to calculations, where the approximate coupled states scattering methods is used.

physics.atm-clus↗

arXiv2023

Imaging Resonance Effects in C + H$_2$ Collisions using a Zeeman Decelerator

An intriguing phenomenon in molecular collisions is the occurrence of scattering resonances, which originate from bound and quasi-bound states supported by the interaction potential at low collision energies. The resonance effects in the scattering behaviour are extraordinarily sensitive to the interaction potential, and their observation provides one of the most stringent tests for theoretical models. We present high-resolution measurements of state-resolved angular scattering distributions for inelastic collisions between Zeeman-decelerated C($^3P_1$) atoms and $\textit{para}$-H$_2$ molecules at collision energies ranging from 77 cm$^{-1}$ down to 0.5 cm$^{-1}$. Rapid variations in the angular distributions were observed that can be attributed to the consecutive reduction of contributing partial waves and effects of scattering resonances. The measurements showed excellent agreement with distributions predicted by $\textit{ab initio}$ quantum scattering calculations. However, discrepancies were found at specific collision energies, which most likely originate from an incorrectly predicted quasi-bound state. These observations provide exciting prospects for further high-precision and low-energy investigations of scattering processes that involve paramagnetic species.

physics.atom-ph↗

arXiv2023

Rovibrational (de-)excitation of H$_{2}$ by He revisited

Collisional (de-)excitation of H$_{2}$ by helium plays an important role in the thermal balance and chemistry of various astrophysical environments, making accurate rate coefficients essential for the interpretation of observations of the interstellar medium. Our goal is to utilize a state-of-the-art potential energy surface (PES) to provide comprehensive state-to-state rate coefficients for He-induced transitions among rovibrational levels of H$_{2}$. We perform quantum scattering calculations for the H$_{2}$-He system and provide state-to-state rate coefficients for 1 089 transitions between rovibrational levels of H$_{2}$ with internal energies up to 15 000 cm$^{-1}$ for temperatures ranging from 20 to 8 000 K. Our results show good agreement with previous calculations for pure rotational transitions between low-lying rotational levels, but we find significant discrepancies for rovibrational processes involving highly-excited rotational and vibrational states. We attribute these differences to two key factors: the broader range of intramolecular distances covered by ab initio points, and the superior accuracy of the PES, resulting from the utilization of the state-of-the-art quantum chemistry methods, compared to the previous lower-level calculations. Radiative transfer calculations performed with the new collisional data indicate that the population of rotational levels in excited vibrational states experiences significant modifications, highlighting the critical need for this updated dataset in models of high-temperature astrophysical environments.

astro-ph.GA↗

arXiv2022

An accurate set of H$_3$O$^+ -$ H$_2$ collisional rate coefficients for non-LTE modelling of warm interstellar clouds

Hydronium (H$_3$O$^+$) was first detected in 1986 in interstellar molecular clouds. It was reported in many galactic diffuse and dense regions, as well as in extragalactic sources. H$_3$O$^+$ plays a major role both in interstellar oxygen and water chemistry. However, despite the large number of H$_3$O$^+$ observations, its collisional excitation was investigated only partially. In the present work we study the state-to-state rotational de-excitation of $ortho$- and $para$-H$_3$O$^+$ in collisions both with $ortho$- and $para$-H$_2$. The cross sections are calculated within the close-coupling formalism using a highly accurate potential energy surface developed for this system. The rate coefficients are computed up to $300$ K kinetic temperature. Transitions between the lowest 21 rotation-inversion states were studied for $para$-H$_3$O$^+$, and the lowest 11 states for $ortho$-H$_3$O$^+$, i.e. all levels with rotational energies below 430 K ($\sim 300$ cm$^{-1}$) are considered (up to $j\leq5$). In order to estimate the impact of the new rate coefficients on the astrophysical models for H$_3$O$^+$, radiative transfer calculations were also carried out. We have examined how the new collisional data affect the line intensities with respect to older data previously used for the interpretation of observations. By analysing all detected transitions we find that our new, accurate rate coefficients have a significant impact (typically within a factor of 2) on radiation temperatures, allowing more accurate estimation of column densities and relative abundances of hydronium, especially in warm molecular clouds, paving the path towards better interpretation of interstellar water and oxygen chemistry.

astro-ph.GA↗

arXiv2022

Hyperfine resolved rate coefficients of HC17O+ with H2 (j = 0)

The formyl cation (HCO+) is one of the most abundant ions in molecular clouds and plays a major role in the interstellar chemistry. For this reason, accurate collisional rate coefficients for the rotational excitation of HCO+ and its isotopes due to the most abundant perturbing species in interstellar environments are crucial for non-local thermal equilibrium models and deserve special attention. In this work, we determined the first hyperfine resolved rate coefficients of HC17O+ in collision with H2 (j=0). Indeed, despite no scattering calculations on its collisional parameters have been performed so far, the HC17O+ isotope assumes a prominent role for astrophysical modelling applications. Computations are based on a new four dimensional (4D) potential energy surface, obtained at the CCSD(T)-F12a/aug-cc-pVQZ level of theory. A test on the corresponding cross section values pointed out that, to a good approximation, the influence of the coupling between rotational levels of H2 can be ignored. For this reason, the H2 collider has been treated as a spherical body and an average of the potential based on five orientations of H2 has been employed for scattering calculations. State-to-state rate coefficients resolved for the HC17O+ hyperfine structure for temperature ranging from 5 to 100 K have been computed using recoupling techniques. This study provides the first determination of HC17O+/H2 inelastic rate coefficients directly computed from full quantum close-coupling equations, thus supporting the reliability of future radiative transfer modellings of HC17O+ in interstellar environments.

astro-ph.GA↗