arXiv subjects

Laurent Wiesenfeld

Publications and source records attributed to Laurent Wiesenfeld.

18 recordsLinked to original sources

arXiv2026

Comprehensive Ab Initio Quantum Computations of CO$_{\rm 2}$-H$_{\rm 2}$ and CO$_{\rm 2}$-He Collisional Properties

We present comprehensive \textsl{ab initio} fully quantum calculations of CO$_{\rm 2}$--H$_{\rm 2}$ and CO$_{\rm 2}$--He collisional properties. Our framework combines CCSD(T) potential-energy-surface calculations with close-coupling dynamical scattering in the \YUMI~framework to derive elastic and inelastic cross sections, rate coefficients, and pressure broadening parameters. We characterize the rotational dependence of the broadening coefficients up to $j=25$ for CO$_{\rm 2}$--H$_{\rm 2}$ and $j=40$ for CO$_{\rm 2}$--He, and their temperature dependence over 40--800 K. We also provide Padé fits as a function of rotational quantum number, enabling extrapolation and integration into spectroscopic databases including HITRAN and HITEMP. The resulting pressure broadening coefficients reproduce available experimental measurements on an absolute scale, without empirical correction factors, and meet the $\sim$10\% precision requirement identified for \textit{JWST}-era exoplanet atmospheric studies. This represents a substantial improvement over previously available parameters, which at higher temperatures ($T>400$ K) can fall outside the desired precision by up to a factor of five. All derivations, computed collisional properties, and database-ready products are provided with this manuscript. Together, these results establish a comprehensive \textsl{ab initio}, parameter-free, fully quantum foundation for CO$_2$ collisional broadening by H$_2$ and He, while demonstrating the transformative potential of the ab-initio approach for next-generation spectroscopic needs across planetary atmospheres, combustion, health sciences, and fusion-plasma diagnostics.

physics.chem-ph↗

arXiv2025

Ab initio quantum dynamics as a scalable solution to the exoplanet opacity challenge: A case study of CO$_2$ in hydrogen atmosphere

Light-matter interactions lie at the heart of our exploration of exoplanetary atmospheres. Interpreting data obtained by remote sensing is enabled by meticulous, time- and resource-consuming work aiming at deepening our understanding of such interactions (i.e., opacity models). Recently, Niraula et al. 2022 pointed out that due primarily to limitations on our modeling of broadening and far-wing behaviors, opacity models needed a timely update for exoplanet exploration in the JWST era, and thus argued for a scalable approach. In this proof-of-concept study, we introduce an end-to-end solution from \textsl{ab initio} calculations to pressure broadening, and use a perturbation framework to identify the need for precision to a level of $\sim$10\%. We focus on the CO$_2$-H$_2$ system as CO$_2$ is a key absorption feature for exoplanet research (primarily in many gas giants) at $\sim$4.3$μ$m as pressure-broadening parameters required for interpreting such observations remain sparse. We compute elastic and inelastic cross-sections for the collision of {ortho-}H$_2$~with CO$_2$, in the ground vibrational state, and at the coupled-channel fully converged level. For scattering energies above $\sim$20~cm$^{-1}$, moderate precision inter-molecular potentials are indistinguishable from high precision ones in cross-sections. Our calculations agree with the currently available measurement within 7\%, i.e., well beyond the precision requirements.

astro-ph.EP↗

arXiv2023

Charge transfer of polyatomic molecules in ion-atom hybrid traps: Stereodynamics in the millikelvin regime

Rate constants for the charge transfer reaction between N${}_{2}$H${}^{+}$ and Rb in the mK regime are measured in an ion-atom hybrid trap and are found to be lower than the Langevin capture limit. Multireference ab initio computation of the potential energy surfaces involved in the reaction reveals that the low-temperature charge transfer is hindered by short-range features highly dependent on the collision angle and is promoted by a deformation of the molecular frame. The present study highlights the importance of polyatomic effects and of stereodynamics in cold molecular ion-neutral collisions.

physics.atom-ph↗

arXiv2021

Quantum nature of molecular vibrational quenching: Water - molecular hydrogen collisions

Rates of conversions of molecular internal energy to and from kinetic energy by means of molecular collision allows to compute collisional line shapes and transport properties of gases. Knowledge of ro-vibrational quenching rates is necessary to connect spectral observations to physical properties of warm astrophysical gasses, including exo-atmospheres. For a system of paramount importance in this context, the vibrational bending mode quenching of H2O by H2, we show here that exchange of vibrational to rotational and kinetic energy remains a quantum process, despite the large numbers of quantum levels involved and the large vibrational energy transfer. The excitation of the quantized rotor of the projectile is by far the most effective ro-vibrational quenching path of water. To do so, we use a fully quantum first principle computation, potential and dynamics, converging it at all stages, in a full coupled channel formalisms. We present here rates for the quenching of the first bendingmode of ortho-H2O by ortho H2, up to 500K, in a fully converged coupled channels formalism.

physics.chem-ph↗

arXiv2018

Modelling the abundance structure of isocyanic acid (HNCO) toward the low-mass solar type protostar IRAS 16293-2422

Isocyanic acid (HNCO), the most stable of the simplest molecules containing the four main elements essential for organic chemistry, has been observed in several astrophysical environments such as molecular clouds, star-forming regions, external galaxies and comets. In this work, we model HNCO spectral line profiles toward the low-mass solar type protostar IRAS 16293$-2$422 observed with the ALMA interferometer, the IRAM, JCMT and APEX single-dish radio telescopes, and the HIFI instrument on board the Herschel Space Observatory. In star-forming environments, the HNCO emission is not always in Local Thermodynamical Equilibrium (LTE). A non-LTE radiative transfer approach is necessary to properly interpret the line profiles, and accurate collisional rate coefficients are needed. Here, we used the RADEX package with a completely new set of collisional quenching rates between HNCO and both ortho-H$_2$ and para-H$_2$ obtained from quantum chemical calculations yielding a novel potential energy surface in the rigid rotor approximation. We find that the lines profiles toward IRAS 16293$-$2422 are very well reproduced if we assume that the HNCO emission arises from a compact, dense and hot physical component associated with the hot corino, a warm component associated with the internal part of the protostellar envelope, and a cold and more extended component associated with the outer envelope. The derived HNCO abundances from our model agree well with those computed with the Nautilus chemical code.

astro-ph.SR↗

arXiv2016

Deuteration of ammonia in the starless core Ophiuchus/H-MM1

Ammonia and its deuterated isotopologues probe physical conditions in dense molecular cloud cores. With the aim of testing the current understanding of the spin-state chemistry of these molecules, we observed spectral lines of NH3, NH2D, NHD2, ND3, and N2D+ towards a dense, starless core in Ophiuchus with the APEX, GBT, and IRAM 30-m telescopes. The observations were interpreted using a gas-grain chemistry model combined with radiative transfer calculations. The chemistry model distinguishes between the different nuclear spin states of light hydrogen molecules, ammonia, and their deuterated forms. High deuterium fractionation ratios with NH2D/NH3=0.4, NHD2/NH2D=0.2, and ND3/NHD2=0.06 were found in the core. The observed ortho/para ratios of NH2D and NHD2 are close to the corresponding nuclear spin statistical weights. The chemistry model can approximately reproduce the observed abundances, but predicts uniformly too low ortho/para-NH2D, and too large ortho/para-NHD2 ratios. The longevity of N2H+ and NH3 in dense gas, which is prerequisite to their strong deuteration, can be attributed to the chemical inertia of N2 on grain surfaces. The discrepancies between the chemistry model and the observations are likely to be caused by the fact that the model assumes complete scrambling in principal gas-phase deuteration reactions of ammonia, which means that all the nuclei are mixed in reactive collisions. If, instead, these reactions occur through proton hop/hydrogen abstraction processes, statistical spin ratios are to be expected. The present results suggest that while the deuteration of ammonia changes with physical conditions and time, the nuclear spin ratios of ammonia isotopologues do not probe the evolutionary stage of a cloud.

astro-ph.GA↗

arXiv2016

Theory of Gas Phase Scattering and Reactivity for Astrochemistry

Because of the very peculiar conditions of chemistry in many astrophysical gases (low densities, mostly low temperatures, kinetics-dominated chemical evolution), great efforts have been devoted to study molecular signatures and chemical evolution. While experiments are being performed in many laboratories, it appears that the efforts directed towards theoretical works are not as strong. This report deals with the present status of chemical physics/physical chemistry theory, for the qualitative and quantitative understanding of kinetics of molecular scattering, being it reactive or inelastic. By gathering several types of expertise, from applied mathematics to physical chemistry, dialog is made possible, as a step towards new and more adapted theoretical frameworks, capable of meeting the theoretical, methodological and numerical challenges of kinetics-dominated gas phase chemistry in astrophysical environments. A state of the art panorama is presented, alongside present-day strengths and shortcomings. However, coverage is not complete, being limited in this report to actual attendance of the workshop. Some paths towards relevant progress are proposed.

astro-ph.IM↗

arXiv2014

Weak maser emission of methyl formate toward Sagittarius B2(N) in the Green Bank Telescope PRIMOS Survey

A non-LTE radiative transfer treatment of cis-methyl formate (HCOOCH3) rotational lines is presented for the first time using a set of theoretical collisional rate coefficients. These coefficients have been computed in the temperature range 5-30 K by combining coupled-channel scattering calculations with a high accuracy potential energy surface for HCOOCH3-He. The results are compared to observations toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. A total of 49 low-lying transitions of methyl formate, with upper levels below 25 K, are identified. These lines are found to probe a presumably cold (~30 K), moderately dense (~1e4 cm-3) and extended region surrounding Sgr B2(N). The derived column density of ~4e14 cm-2 is only a factor of ~10 larger than the column density of the trans conformer in the same source. Provided that the two conformers have the same spatial distribution, this result suggests that strongly non-equilibrium processes must be involved in their synthesis. Finally, our calculations show that all detected emission lines with a frequency below 30 GHz are (collisionally pumped) weak masers amplifying the continuum of Sgr B2(N). This result demonstrates the importance and generality of non-LTE effects in the rotational spectra of complex organic molecules at centimetre wavelengths.

astro-ph.GA↗

arXiv2013

CII in the Interstellar Medium: Excitation by H2 Revisited

C$^+$ is a critical constituent of many regions of the interstellar medium, as it can be a major reservoir of carbon and, under a wide range of conditions, the dominant gas coolant. Emission from its 158$μ$m fine structure line is used to trace the structure of photon dominated regions in the Milky Way and is often employed as a measure of the star formation rate in external galaxies. Under most conditions, the emission from the single [CII] line is proportional to the collisional excitation rate coefficient. We here used improved calculations of the deexcitation rate of [CII] by collisions with H$_2$ to calculate more accurate expressions for interstellar C$^+$ fine structure emission, its critical density, and its cooling rate. The collision rates in the new quantum calculation are $\sim$ 25% larger than those previously available, and narrow the difference between rates for excitation by atomic and molecular hydrogen. This results in [CII] excitation being quasi-independent of the molecular fraction and thus dependent only on the total hydrogen particle density. A convenient expression for the cooling rate at temperatures between 20 K and 400 K, assuming an LTE H$_2$ ortho to para ration is $Λ({\rm LTE~OPR}) = \left(11.5 + 4.0\,e^{-100\,\mathrm K/T^{\rm kin}}\right)\;e^{-91.25\,\mathrm K/T^{\rm kin}}\,n ({\rm C}^{+})\,n({\rm H}_2)\times 10^{-24}\;{\rm ergs}~{\rm cm}^{-3}~{\rm s}^{-1}$. The present work should allow more accurate and convenient analysis of the [\CII] line emission and its cooling.

astro-ph.GA↗

arXiv2013

Rotational quenching of H2CO by molecular hydrogen: cross-sections, rates, pressure broadening

We compute the rotational quenching rates of the first 81 rotational levels of ortho- and para-H2CO in collision with ortho- and para-H2, for a temperature range of 10-300 K. We make use of the quantum close-coupling and coupled-states scattering methods combined with the high accuracy potential energy surface of Troscompt et al. (2009a). Rates are significantly different from the scaled rates of H2CO in collision with He; consequently, critical densities are noticeably lower. We compare a full close- coupling computation of pressure broadening cross sections with experimental data and show that our results are compatible with the low temperature measurements of Mengel & De Lucia (2000), for a spin temperature of H2 around 50 K.

astro-ph.SR↗

arXiv2012

Water ice deuteration: a tracer of the chemical history of protostars

Context. Millimetric observations have measured high degrees of molecular deuteration in several species seen around low-mass protostars. The Herschel Space Telescope, launched in 2009, is now providing new measures of the deuterium fractionation of water, the main constituent of interstellar ices. Aims. We aim at theoretically studying the formation and the deuteration of water, which is believed to be formed on interstellar grain surfaces in molecular clouds. Methods. We used our gas-grain astrochemical model GRAINOBLE, which considers the multilayer formation of interstellar ices. We varied several input parameters to study their impact on water deuteration. We included the treatment of ortho- and para-states of key species, including H2, which affects the deuterium fractionation of all molecules. The model also includes relevant laboratory and theoretical works on the water formation and deuteration on grain surfaces. In particular, we computed the transmission probabilities of surface reactions using the Eckart model, and we considered ice photodissociation following molecular dynamics simulations. Results. The use of a multilayer approach allowed us to study the influence of various parameters on the abundance and the deuteration of water. Deuteration of water is found to be very sensitive to the ortho-to-para ratio of H2 and to the total density, but it also depends on the gas/grain temperatures and the visual extinction of the cloud. Since the deuteration is very sensitive to the physical conditions, the comparison with sub-millimetric observation towards the low-mass protostar IRAS 16293 allows us to suggest that water ice is formed together with CO2 in molecular clouds with limited density, whilst formaldehyde and methanol are mainly formed in a later phase, where the condensation becomes denser and colder.

astro-ph.GA↗

arXiv2012

Radiation thermo-chemical models of protoplanetary discs. IV Modelling CO ro-vibrational emission from Herbig Ae discs

The carbon monoxide rovibrational emission from discs around Herbig Ae stars and T Tauri stars with strong ultraviolet emissions suggests that fluorescence pumping from the ground X1 Sigma+ to the electronic A1 Pi state of CO should be taken into account in disc models. We implemented a CO model molecule that includes up to 50 rotational levels within nine vibrational levels for the ground and A excited states in the radiative photochemical code ProDiMo. We took CO collisions with hydrogen molecules, hydrogen atoms, helium, and electrons into account. We estimated the missing collision rates using standard scaling laws and discussed their limitations. UV fluorescence and IR pumping impact on the population of ro-vibrational v > 1 levels. The v = 1 rotational levels are populated at rotational temperatures between the radiation temperature around 4.6 micron and the gas kinetic temperature. The UV pumping efficiency increases with decreasing disc mass. The consequence is that the vibrational temperatures, which measure the relative populations between the vibrational levels, are higher than the disc gas kinetic temperatures (suprathermal population). Rotational temperatures from fundamental transitions derived using optically thick 12CO lines do not reflect the gas kinetic temperature. CO pure rotational levels with energies lower than 1000 K are populated in LTE but are sensitive to a number of vibrational levels included in the model. The 12CO pure rotational lines are highly optically thick for transition from levels up to Eupper=2000 K. (abridged)

astro-ph.GA↗

arXiv2012

A study of deuterated water in the low-mass protostar IRAS16293-2422

The HDO/H2O ratio is a powerful diagnostic to understand the evolution of water from the first stages of star formation to the formation of planets and comets. Our aim is to determine precisely the abundance distribution of HDO towards the low-mass protostar IRAS16293-2422 and learn more about the water formation mechanisms by determining the HDO/H2O abundance ratio. A spectral survey of the source IRAS16293-2422 was carried out in the framework of the CHESS Herschel Key program with the HIFI instrument, allowing the detection of numerous HDO lines. Other transitions have been observed previously with ground-based telescopes. The spherical Monte Carlo radiative transfer code RATRAN was used to reproduce the observed line profiles of HDO by assuming an abundance jump. To determine the H2O abundance throughout the envelope, a similar study was made of the H2-18O observed lines, as the H2O main isotope lines are contaminated by the outflows. We derive an inner HDO abundance of 1.7e-7 and an outer HDO abundance of 8e-11. To reproduce the HDO absorption lines, it is necessary to add an absorbing layer in front of the envelope. It may correspond to a water-rich layer created by the photodesorption of the ices at the edges of the molecular cloud. The HDO/H2O ratio is ~1.4-5.8% in the hot corino whereas it is ~0.2-2.2% in the outer envelope. It is estimated at ~4.8% in the added absorbing layer. Although it is clearly higher than the cosmic D/H abundance, the HDO/H2O ratio remains lower than the D/H ratio derived for other deuterated molecules observed in the same source. The similarity of the ratios derived in the hot corino and in the added absorbing layer suggests that water formed before the gravitational collapse of the protostar, contrary to formaldehyde and methanol, which formed later once the CO molecules had depleted on the grains.

astro-ph.GA↗

arXiv2010

Collisional excitation of doubly deuterated ammonia NHD2 by para-H2

Collisional de-excitation rates of partially deuterated molecules are different from the fully hydrogenated species because of lowering of symmetry. We compute the collisional (de)excitation rates of ND2H by ground state para-H2, extending the previous results for He- lium. We describe the changes in the potential energy surface of NH3- H2 involved by the pres- ence of two deuterium nuclei. Cross sections are calculated within the full close-coupling ap- proach and augmented with coupled-state calculations. Collisional rate coefficients are given between 5 and 35 K, a range of temperatures which is relevant to cold interstellar conditions. We find that the collisional rates of ND2H by H2 are about one order of magnitude higher than those obtained with Helium as perturber. These results are essential to radiative transfer modelling and will allow to interpret the millimeter and submillimeter detections of ND2H with better constraints than previously.

astro-ph.GA↗

arXiv2010

Ab initio computation of the broadening of water rotational lines by molecular hydrogen

Theoretical cross sections for the pressure broadening by hydrogen of rotational transitions of water are compared to the latest available measurements in the temperature range 65-220 K. A high accuracy interaction potential is employed in a full close coupling calculation. A good agreement with experiment is observed above ~80 K while the sharp drop observed experimentally at lower temperatures is not predicted by our calculations. Possible explanations for this discrepancy include the failure of the impact approximation and the possible role of ortho-to-para conversion of H2.

physics.chem-ph↗

arXiv2009

On the robustness of the ammonia thermometer

Ammonia inversion lines are often used as probes of the physical conditions in the dense ISM. The excitation temperature between the first two para metastable (rotational) levels is an excellent probe of the gas kinetic temperature. However, the calibration of this ammonia thermometer depends on the accuracy of the collisional rates with H2. Here we present new collisional rates for ortho-NH3 and para-NH3 colliding with para-H2 (J=0) and we investigate the effects of these new rates on the excitation of ammonia. Scattering calculations employ a new, high accuracy, potential energy surface computed at the coupled-cluster CCSD(T) level with a basis set extrapolation procedure. Rates are obtained for all transitions involving ammonia levels with J <= 3 and for kinetic temperatures in the range 5-100 K. We find that the calibration curve of the ammonia thermometer -- which relates the observed excitation temperature between the first two para metastable levels to the gas kinetic temperature -- does not change significantly when these new rates are used. Thus, the calibration of ammonia thermometer appears to be robust. Effects of the new rates on the excitation temperature of inversion and rotation-inversion transitions are also found to be small.

astro-ph.GA↗

arXiv2006

Rotational Excitation of HC_3N by H_2 and He at low temperatures

Rates for rotational excitation of HC3N by collisions with He atoms and H2 molecules are computed for kinetic temperatures in the range 5-20K and 5-100K, respectively. These rates are obtained from extensive quantum and quasi-classical calculations using new accurate potential energy surfaces (PES).

physics.chem-ph↗

arXiv1998

Topological aspects of chaotic scattering in higher dimensions

We investigate the topological properties of invariant sets associated with the dynamics of scattering systems with three or more degrees of freedom. We show that the asymptotic separation of one degree of freedom from the rest in the asymptotic regime, a common property in a large class of scattering models, defines a dynamical object with phase space separating invariant manifolds and an invariant set with larger dimension than that of the set defined by bounded orbits. In particular, the set of typical periodic orbits involving all the degrees of freedom of the system form a nowhere dense subset of the large invariant set.

chao-dyn↗