arXiv subjects

Olivier Pirali

Publications and source records attributed to Olivier Pirali.

10 recordsLinked to original sources

arXiv2026

High-Resolution Infrared Spectroscopy and ASAP Analysis of Cyclopentadiene: The Vibrational Modes below 860 cm$^{-1}$ and the $ν_{21}$ Mode at 961 cm$^{-1}$

The spectroscopic fingerprints of vibrationally excited states of astronomical molecules are interesting for multiple reasons. They are excellent temperature probes of the corresponding astronomical regions and are thought to be the origin of many unknown lines in astronomical survey spectra. Rovibrational spectra provide accurate vibrational energies and can guide subsequent pure rotational studies. The Automated Spectral Assignment Procedure (ASAP) greatly simplifies the rovibrational analysis when the rotational spectrum of either the upper or lower vibrational state is known with a high degree of accuracy (e.g., from a rotational analysis). Here, we present a new implementation of ASAP for the analysis of cyclopentadiene, a cyclic pure hydrocarbon that has already been detected astronomically toward the cold core of the Taurus Molecular Cloud. Using the synchrotron radiation extracted by the AILES beamline of the SOLEIL facility, we recorded mid- and far-infrared high-resolution spectra of cyclopentadiene. We analyzed the rovibrational spectrum of the $ν_{21}$ fundamental (961 cm$^{-1}$) with ASAP and used ASAP$^2$ to determine the vibrational energies of the eight vibrational modes below 860 cm$^{-1}$. ASAP$^2$ is an extension of ASAP for rovibrational bands where the rotational structures of the lower and upper states are known with high accuracy, leaving only the vibrational band center to be determined. The presented rovibrational fingerprints agree with the results from pure rotational spectroscopy, demonstrating the efficiency and reliability of our new ASAP implementation.

physics.chem-ph↗

arXiv2025

Evidence for electron spin-torsion coupling in the rotational spectrum of the CH$_3$CO radical

Open-shell non-rigid molecular systems exhibiting an internal rotation are likely candidates for a coupling between the spin angular momentum of the unpaired electron and the torsional motion. This electron spin-torsion coupling lacked both an experimental validation and a theoretical modeling. Here, the first experimental observation of the electron spin-torsion coupling is reported analyzing the pure rotational spectrum at millimeter wavelengths of the CH$_3$CO radical, a $^2Σ$ open-shell molecule displaying an internal rotation of its methyl group. To account for this coupling, a specific Hamiltonian incorporating the rotational, torsional, and electronic degrees of freedom is developed and allows us to reproduce the experimental spectrum. The present demonstration of the electron spin-torsion coupling will undoubtedly be key to future investigations of large open-shell molecules exhibiting a complex internal dynamics.

physics.chem-ph↗

arXiv2025

Laboratory rotational spectroscopy leads to the first interstellar detection of singly deuterated methyl mercaptan (CH$_{2}$DSH)

We report an extensive rotational spectroscopic analysis of singly deuterated methyl mercaptan (CH$_{2}$DSH) using both millimeter and far-infrared synchrotron spectra to achieve a global torsional analysis of the three lowest torsional substates (e$_{0}$, e$_{1}$, and o$_{1}$) of this non-rigid species. A fit including 3419 millimeter wave transitions along with 43 infrared torsional subband centers was performed with root mean square deviations of 0.233 MHz and 0.270 cm$^{-1}$, respectively, resulting in 68 fit parameters. A spectroscopic catalogue built from this analysis for a temperature of 125 K has led to the first interstellar detection of CH$_{2}$DSH towards the Solar-like protostar IRAS 16293-2422 B. We report the identification of 46 transitions, including eight relatively unblended lines, resulting in a derived column density of (3.0$\pm$0.3)$\times$10$^{14}$ cm$^{-2}$. The column density ratio for HDCS/CH$_{2}$DSH compared to HDCO/CH$_{2}$DOH suggests a difference in the interstellar chemistry between the sulphur and oxygen complex organics, in particular a different link between H$_{2}$CO and CH$_{3}$OH and between H$_{2}$CS and CH$_{3}$SH. This is the first interstellar detection of a deuterated sulphur-bearing COM and therefore an important step into understanding the chemical origin of sulphur-based prebiotics.

astro-ph.GA↗

arXiv2024

Submillimeter-wave spectroscopy of the CH$_3$O radical

The methoxy radical, CH$_3$O, has long been studied experimentally and theoretically by spectroscopists because it displays a weak Jahn-Teller effect in its electronic ground state, combined with a strong spin-orbit interaction. In this work, we report an extension of the measurement of the pure rotational spectrum of the radical in its vibrational ground state in the submillimeter-wave region (350$-$860 GHz). CH$_3$O was produced by H-abstraction from methanol using F-atoms, and its spectrum was probed in absorption using an association of source-frequency modulation and Zeeman modulation spectroscopy. All the observed transitions together with available literature data in $v = 0$ were combined and fit using an effective Hamiltonian allowing to reproduce the data at their experimental accuracy. The newly measured transitions involve significantly higher frequencies and rotational quantum numbers than those reported in the literature ($f < 860$ GHz and $N \leq 15$ instead of 272 GHz and 7, respectively) which results in significant improvements in the spectroscopic parameters determination. The present model is well constrained and allows a reliable calculation of the rotational spectrum of the radical over the entire microwave to submillimeter-wave domain. It can be used with confidence for future searches of CH$_3$O in the laboratory and the interstellar medium.

astro-ph.GA↗

arXiv2024

Unveiling gas phase H2NCO radical: Laboratory rotational spectroscopy and interstellar search toward IRAS 16293-2422

Context. The carbamoyl radical (H2NCO) is believed to play a central role in the ice-grain chemistry of crucial interstellar complex organic molecules as formamide and acetamide. Yet, little is known about this radical that remains elusive in laboratory gas-phase experiments. Aims. In order to enable interstellar searches of H2NCO, we have undertaken a mandatory laboratory characterisation of its pure rotational spectrum. Methods. We report the gas-phase laboratory detection of H2NCO, produced by H-atom abstraction from formamide, using pure rotational spectroscopy at millimetre and submillimetre wavelengths. Millimetre-wave data were acquired using chirped-pulse Fourier-transform spectroscopy while submillimetre-wave ones were obtained using Zeeman-modulated spectroscopy. Experimental measurements were guided by quantum-chemical calculations at the $ω$B97X-D/cc-pVQZ level of theory. Interstellar searches for the radical have been undertaken on the Protostellar Interferometric Line Survey (PILS) towards the solar-type protostar IRAS 16293-2422. Results. From the assignment and fit of experimental transitions up to 660 GHz, reliable spectroscopic parameters for H2NCO in its ground vibrational state have been derived, enabling accurate spectral predictions. No transitions of the radical were detected on the PILS survey. The inferred upper limit shows that H2NCO abundance is at least 60 times below that of formamide and 160 times below that of HNCO in this source; a value that is in agreement with predictions from a physico-chemical model of this young protostar.

astro-ph.GA↗

arXiv2023

The Bending of C$_3$: Experimentally Probing the $l$-type Doubling and Resonance

C$_3$, a pure carbon chain molecule that has been identified in different astronomical environments, is considered a good probe of kinetic temperatures through observation of transitions involving its low-lying bending mode ($ν_2$) in its ground electronic state. The present laboratory work aims to investigate this bending mode with multiple quanta of excitation by combining recordings of high resolution optical and infrared spectra of C$_3$ produced in discharge experiments. The optical spectra of rovibronic (A $^1Π_u -$ X $^1Σ_g^+$) transitions have been recorded by laser induced fluorescence spectroscopy using a single longitude mode optical parametric oscillator as narrow bandwidth laser source at the University of Science and Technology of China. 36 bands originating from X(0$v_2$0), $v_2 = 0-5$, are assigned. The mid-infrared spectrum of the rovibrational $ν_3$ band has been recorded by Fourier-transform infrared spectroscopy using a globar source on the AILES beamline of the SOLEIL synchrotron facility. The spectrum reveals hot bands involving up to 5 quanta of excitation in $ν_2$. From combining analyses of all the presently recorded spectra and literature data, accurate rotational parameters and absolute energy levels of C$_3$, in particular for states involving the bending mode, are determined. A single PGOPHER file containing all available data involving the X and A states (literature and present study) is used to fit all the data. The spectroscopic information derived from this work enables new interstellar searches for C$_3$, not only in the infrared and optical regions investigated here but also notably in the $ν_2$ band region (around 63 cm$^{-1}$) where vibrational satellites can now be accurately predicted. This makes C$_3$ a universal diagnostic tool to study very different astronomical environments, from dark and dense to translucent clouds.

astro-ph.GA↗

arXiv2021

A rotational and vibrational investigation of phenylpropiolonitrile (C$_6$H$_5$C$_3$N)

The evidence for benzonitrile (C$_6$H$_5$CN}) in the starless cloud core TMC-1 makes high-resolution studies of other aromatic nitriles and their ring-chain derivatives especially timely. One such species is phenylpropiolonitrile (3-phenyl-2-propynenitrile, C$_6$H$_5$C$_3$N), whose spectroscopic characterization is reported here for the first time. The low resolution (0.5 cm$^{-1}$) vibrational spectrum of C$_6$H$_5$C$_3$N} has been recorded at far- and mid-infrared wavelengths (50 - 3500 cm$^{-1}$) using a Fourier Transform interferometer, allowing for the assignment of band centers of 14 fundamental vibrational bands. The pure rotational spectrum of the species has been investigated using a chirped-pulse Fourier transform microwave (FTMW) spectrometer (6 - 18 GHz), a cavity enhanced FTMW instrument (6 - 20 GHz), and a millimeter-wave one (75 - 100 GHz, 140 - 214 GHz). Through the assignment of more than 6200 lines, accurate ground state spectroscopic constants (rotational, centrifugal distortion up to octics, and nuclear quadrupole hyperfine constants) have been derived from our measurements, with a plausible prediction of the weaker bands through calculations. Interstellar searches for this highly polar species can now be undertaken with confidence since the astronomically most interesting radio lines have either been measured or can be calculated to very high accuracy below 300 GHz.

astro-ph.GA↗

arXiv2020

Submillimetre and far-infrared spectroscopy of monodeuterated amidogen radical (NHD): improved rest-frequencies for astrophysical observations

Observations of ammonia in interstellar environments have revealed high levels of deuteration, and all its D-containing variants, including ND$_3$, have been detected in cold prestellar cores and around young protostars. The observation of these deuterated isotopologues is very useful to elucidate the chemical and physical processes taking place during the very early stages of star formation, as the abundance of deuterated molecules is highly enhanced in dense and cold gas. Nitrogen hydride radicals are key species lying at the very beginning of the reaction pathway leading to the formation of NH$_3$ and organic molecules of pre-biotic interest, but relatively little information is known about their D-bearing isotopologues. To date, only ND has been detected in the interstellar gas. To aid the identification of further deuterated nitrogen radicals, we have thoroughly re-investigated the rotational spectrum of NHD employing two different instruments: a frequency-modulation submillimetre spectrometer operating in the THz region and a synchrotron-based Fourier Transform infrared spectrometer operating in the 50-240 cm$^{-1}$ wavelength range. NHD was produced in a plasma of NH$_3$ and D$_2$. A wide range of rotational energy levels has been probed thanks to the observation of high $N$ (up to 15) and high $K_a$ (up to 9) transitions. A global analysis including our new data and those already available in the literature has provided a comprehensive set of very accurate spectroscopic parameters. A highly reliable line catalogue has been generated to assist archival data searches and future astronomical observations of NHD at submillimetre and THz regimes.

astro-ph.GA↗

arXiv2020

Conformational Landscape of Oxygen-Containing Naphthalene Derivatives

Polycyclic aromatic compounds (PACs) constitute an important class of molecules found in various environments and are considered important pollutants of the Earth's atmosphere. In particular, functionalization of PACs modify the ring aromaticity, which greatly influences the chemical reactivity of these species. In this work we studied several oxygen-containing PACs, relevant to atmospheric chemistry. We investigated the conformational landscape of four naphthalene-derivative molecules -- namely ,1- and 2-hydroxynaphthalene and 1- and 2-naphthaldehyde -- by means of rotational and vibrational spectroscopy supported by quantum chemical calculations. For 1-hydroxynaphthalene and 1-naphthaldehyde, intramolecular hydrogen bonding and steric effects drive the conformational preferences while for 2-hydroxynaphthalene and 2-naphthaldehyde, the charge distributions allow us to understand the conformational landscape. This work not only demonstrates how the localization of the substitution group in the ring influences the conformational relative energies and but also constitutes a step toward a better understanding of the different chemical reactivity of such functionalized PACs.

physics.chem-ph↗

arXiv2018

Far infrared measurements of absorptions by CH4+CO2 and H2+CO2 mixtures and implications for greenhouse warming on early Mars

We present an experimental study of the absorption, between 40 and 640 cm$^{-1}$, by CO$_2$, CH$_4$ and H$_2$ gases as well as by H$_2$+CO$_2$ and CH$_4$+CO$_2$ mixtures at room temperature. A Fourier transform spectrometer associated to a multi-pass cell, whose optics were adjusted to obtain a 152 m pathlength, were used to record transmission spectra at total pressures up to about 0.98 bar. These measurements provide information concerning the collision-induced absorption (CIA) bands as well as about the wing of the CO$_2$ 15 $μ$m band. Our results for the CIAs of pure gases are, within uncertainties, in agreement with previous determinations, validating our experimental and data analysis procedures. We then consider the CIAs by H$_2$+CO$_2$ and CH$_4$+CO$_2$ and the low frequency wing of the pure CO$_2$ 15 $μ$m band, for which there are, to our knowledge, no previous measurements. We confirm experimentally the theoretical prediction of Wordsworth et al. 2017 that the H$_2$+CO$_2$ and CH$_4$+CO$_2$ CIAs are significantly stronger in the 50-550 cm$^{-1}$ region than those of H$_2$+N$_2$ and CH$_4$+N$_2$, respectively. However, we find that the shape and the strength of these recorded CIAs differ from the aforementioned predictions. For the pure CO$_2$ line-wings, we show that both the $χ$-factor deduced from measurements near 4 $μ$m and a line-mixing model very well describe the observed strongly sub-Lorentzian behavior in the 500-600 cm$^{-1}$ region. These experimental results open renewed perspectives for studies of the past climate of Mars and extrasolar analogues.

astro-ph.EP↗