arXiv subjects

Annemieke Petrignani

Publications and source records attributed to Annemieke Petrignani.

9 recordsLinked to original sources

arXiv2024

Photodissociation and induced chemical asymmetries on ultra-hot gas giants. A case study of HCN on WASP-76 b

Recent observations have resulted in the detection of chemical gradients on ultra-hot gas giants. Notwithstanding their high temperature, chemical reactions in ultra-hot atmospheres may occur in disequilibrium, due to vigorous day-night circulation and intense UV radiation from their stellar hosts. The goal of this work is to explore whether photochemistry is affecting the composition of ultra-hot giant planets, and if it can introduce horizontal chemical gradients. In particular, we focus on hydrogen cyanide (HCN) on WASP-76 b, as it is a photochemically active molecule with a reported detection on only one side of this planet. We use a pseudo-2D chemical kinetics code to model the chemical composition of WASP-76 b along its equator. Our approach improves on chemical equilibrium models by computing vertical mixing, horizontal advection, and photochemistry. We find that production of HCN is initiated through thermal and photochemical dissociation of CO and N$_2$ on the day side of WASP-76 b. The resulting radicals are subsequently transported to the night side via the equatorial jet stream, where they recombine into different molecules. This process results in an HCN gradient with a maximal abundance on the planet's morning limb. We verified that photochemical dissociation is a necessary condition for this mechanism, as thermal dissociation alone proves insufficient. Other species produced via night-side disequilibrium chemistry are SO$_2$ and S$_2$. Our model acts as a proof of concept for chemical gradients on ultra-hot exoplanets. We demonstrate that even ultra-hot planets can exhibit disequilibrium chemistry and recommend that future studies do not neglect photochemistry in their analyses of ultra-hot planets.

astro-ph.EP↗

arXiv2024

PDRs4All VII. The 3.3 $μ$m aromatic infrared band as a tracer of physical properties of the ISM in galaxies

Aromatic infrared bands (AIBs) are a set of broad emission bands at 3.3, 6.2, 7.7, 8.6, 11.2, and 12.7 $μ$m, seen in the infrared spectra of most galaxies. With JWST, the 3.3 $μ$m AIB can in principle be detected up to a redshift of $\sim$ 7. Relating the evolution of the 3.3 $μ$m AIB to local physical properties of the ISM is thus of paramount importance. By applying a dedicated machine learning algorithm to JWST NIRSpec observations of the Orion Bar photodissociation region obtained as part of the PDRs4All Early Release Science (ERS) program, we extracted two template spectra capturing the evolution of the AIB-related emission in the 3.2-3.6 $μ$m range, which includes the AIB at 3.3 $μ$m and its main satellite band at 3.4 $μ$m. In the Orion Bar, we analyze the spatial distribution of the templates and their relationship with the fluorescent emission of H$_2$ in the near infrared. We find that one template ("AIB$_{\rm Irrad}$") traces regions of neutral atomic gas with strong far-UV fields, while the other template ("AIB$_{\rm Shielded}$") corresponds to shielded regions with lower FUV fields and a higher molecular gas fraction. We then show that these two templates can be used to fit the NIRSpec AIB-related spectra of nearby galaxies. The relative weight of the two templates (AIB$_{\rm Irrad/Shielded}$) is a tracer of the radiative feedback from massive stars on the ISM. We derive an estimate of AIB$_{\rm Irrad/Shielded}$ in a $z$ = 4.22 lensed galaxy, and find that it has a lower value than for local galaxies. This pilot study illustrates how a detailed analysis of AIB emission in nearby regions can be used to probe the physical conditions of the extragalactic ISM.

astro-ph.GA↗

arXiv2021

Gas-phase spectroscopy of photostable PAH ions from the mid- to far-infrared

We present gas-phase InfraRed Multiple Photon Dissociation (IRMPD) spectroscopy of cationic phenanthrene, pyrene, and perylene over the 100$-$1700 cm$^{-1}$ (6-95 $μ$m) spectral range. This range covers both local vibrational modes involving C$-$C and C$-$H bonds in the mid-IR, and large-amplitude skeletal modes in the far-IR. The experiments were done using the 7T Fourier-Transform Ion Cyclotron Resonance (FTICR) mass spectrometer integrated in the Free-Electron Laser for Intra-Cavity Experiments (FELICE), and findings were complemented with Density Functional Theory (DFT) calculated harmonic and anharmonic spectra, matching the experimental spectra well. The experimental configuration that enables this sensitive spectroscopy of the strongly-bound, photo-resistant Polycyclic Aromatic Hydrocarbons (PAHs) over a wide range can provide such high photon densities that even combination modes with calculated intensities as low as 0.01 km$\cdot$mol$^{-1}$ near 400 cm$^{-1}$ (25 $μ$m) can be detected. Experimental frequencies from this work and all currently available IRMPD spectra for PAH cations were compared to theoretical frequencies from the NASA Ames PAH IR Spectroscopic Database to verify predicted trends for far-IR vibrational modes depending on PAH shape and size, and only a relatively small redshift (6$-$11 cm$^{-1}$) was found between experiment and theory. The absence of spectral congestion and the drastic reduction in bandwidth with respect to the mid-IR make the far-IR fingerprints viable candidates for theoretical benchmarking, which can aid in the search for individual large PAHs in the interstellar medium.

physics.chem-ph↗

arXiv2021

IRMPD spectroscopy of a PAH cation using FELICE: The infrared spectrum and photodissociation of dibenzo[a,l]pyrene

We present the experimental InfraRed Multiple Photon Dissociation (IRMPD) spectrum and fragmentation mass spectrum of the irregular, cationic PAH dibenzo[a,l]pyrene (C$_{24}$H$_{14}^+$) in the 6-40 $μ$m / 250-1650 cm$^{-1}$ range. The use of the the Free-Electron Laser for IntraCavity Experiments (FELICE) enabled us to record its Far-InfraRed (FIR) spectrum for the first time. We aim to understand how irregularity affects the infrared spectrum and fragmentation chemistry of PAHs. Dibenzo[a,l]pyrene is an asymmetric, non-planar molecule, for which all vibrational modes are in principle IR-active. Calculated harmonic Density Function Theory (DFT) and anharmonic Density Functional based Tight Binding Molecular Dynamics (DFTB-MD) spectra show a large wealth of bands, which match the experiment well, but with a few differences. The periphery of the molecule contains several edge geometries, but out of all possible modes in the 11-14 $μ$m out-of-plane C-H bending region, only one band at 13.5 $μ$m is prominent. This fact and the richness of the C-C stretching range make irregular PAHs a possible contributor to D-class interstellar spectra. The fragmentation mass spectra reveal facile 2H-loss and no [2C, 2H]-loss, which is attributed to the sterically hindered, non-planar cove region, which could protect irregular PAHs from radiation damage.

physics.chem-ph↗

arXiv2016

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons in the 3 μm region: Role of periphery

In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO program that incorporates a Fermi resonance treatment utilizing intensity redistribution. We show that the 3 μm region is dominated by the effects of anharmonicity, resulting in many more bands than would have been expected in a purely harmonic approximation. Importantly, we find that anharmonic spectra as calculated by SPECTRO are in good agreement with the experimental spectra. Together with previously reported high-resolution spectra of linear acenes, the present spectra provide us with an extensive dataset of spectra of PAHs with a varying number of aromatic rings, with geometries that range from open to highly-condensed structures, and featuring CH groups in all possible edge configurations. We discuss the astrophysical implications of the comparison of these spectra on the interpretation of the appearance of the aromatic infrared 3 μm band, and on features such as the two-component emission character of this band and the 3 μm emission plateau.

astro-ph.GA↗

arXiv2015

High-resolution IR absorption spectroscopy of polycyclic aromatic hydrocarbons: the realm of anharmonicity

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micron CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (~4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilises intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3 micron band are discussed.

astro-ph.GA↗

arXiv2015

Visible line intensities of the triatomic hydrogen ion from experiment and theory

The visible spectrum of H3+ is studied using high-sensitivity action spectroscopy in a cryogenic radiofrequency multipole trap. Advances are made to measure the weak ro-vibrational transitions from the lowest rotational states of H3+ up to high excitation energies providing visible line intensities and, after normalisation to an infrared calibration line, the corresponding Einstein $B$ coefficients. {\it Ab initio} predictions for the Einstein $B$ coefficients are obtained from a highly precise dipole moment surface of H3+ and found to be in excellent agreement, even in the region where states have been classified as chaotic.

physics.chem-ph↗

arXiv2010

Resonant structure of low-energy H3+ dissociative recombination

New high-resolution dissociative recombination rate coefficients of rotationally cool and hot H3+ in the vibrational ground state have been measured with a 22-pole trap setup and a Penning ion source, respectively, at the ion storage ring TSR. The experimental results are compared with theoretical calculations to explore the dependence of the rate coefficient on ion temperature and to study the contributions of different symmetries to probe the rich predicted resonance spectrum. The break-up energy was investigated by fragment imaging to derive internal temperatures of the stored parent ions under differing experimental conditions. A systematic experimental assessment of heating effects is performed which, together with a survey of other recent storage-ring data, suggests that the present rotationally cool rate-coefficient measurement was performed at 380^{+50}_{-130} K and that this is the lowest rotational temperature so far realized in storage-ring rate-coefficient measurements on H3+. This partially supports the theoretical suggestion that higher temperatures than assumed in earlier experiments are the main cause for the large gap between the experimental and theoretical rate coefficients. For the rotationally hot rate-coefficient measurement a temperature of below 3250K is derived. From these higher-temperature results it is found that increasing the rotational ion temperature in the calculations cannot fully close the gap between the theoretical and experimental rate coefficients.

physics.chem-ph↗

arXiv2008

Chemical probing spectroscopy of H3+ above the barrier to linearity

We have performed chemical probing spectroscopy of H3+ ions trapped in a cryogenic 22-pole ion trap. The ions were buffer-gas cooled to 55K by collisions with helium and argon. Excitation to states above the barrier to linearity was achieved by a Ti:Sa laser operated between 11300 and 13300 cm-1. Subsequent collisions of the excited H3+ ions with argon lead to the formation of ArH+ ions that were detected by a quadrupole mass spectrometer with high sensitivity. We report the observation of 17 previously unobserved transitions to states above the barrier to linearity. Comparison to theoretical calculations suggests that the transition strengths of some of these lines are more than five orders of magnitude smaller than those of the fundamental band, which renders them - to the best of our knowledge - the weakest H3+ transitions observed to date.

physics.chem-ph↗