Electronic spectroscopy of 1-cyanonaphthalene cation for astrochemical consideration

Context. Polycyclic aromatic hydrocarbons (PAHs) are believed to be the carriers of the aromatic infrared bands and have been proposed as candidates to explain other astronomical phenomena such as diffuse interstellar bands (DIBs). The first aromatic structures possessing more than one ring, 1- and 2-cyanonaphthalene (CNN), were recently detected by rotational spectroscopy in the dense molecular cloud TMC-1. Laboratory investigations have indicated that due to fast and efficient relaxation through recurrent fluorescence (RF), CNN+ may be photostable in the harsh conditions of the lower density, more diffuse regions of the interstellar medium (ISM) exposed to ultraviolet (UV) radiation. As a result, it has been suggested that the widely held belief that small PAHs present in these regions are dissociated may need to be revisited. If 1-CNN+ is able to survive in the diffuse ISM it may contribute to the population of 1-CNN observed in TMC-1. To investigate the abundance of 1-CNN+ in diffuse clouds, laboratory spectroscopy is required. The present work concerns the electronic spectroscopy of 1-CNN+ in absorption and the search for its spectroscopic fingerprints in diffuse clouds. Aims. The aim is to obtain laboratory data on the electronic transitions of gas-phase 1-CNN+ under conditions appropriate for comparison with DIBs and assess abundance in diffuse clouds. Methods. Spectroscopic experiments are carried out using a cryogenic ion trapping apparatus in which gas-phase 1-CNN+ is cooled to temperatures below 10 K through buffer gas cooling. Calculations are carried out using time-dependent density-functional theory. Results. Experimental and theoretical data on the D2 ← D0 and D3 ← D0 electronic transitions of 1-CNN+ are reported. The former transition has a calculated oscillator strength of f = 0.075 and possesses a pattern dominated by its origin band. The origin band is located at 7343 Å and has a full width at half maximum of 28 Å. In observational data, this falls in a region polluted by telluric water lines, hindering assessment of its abundance. Conclusions. Space-based observations are required to search for the spectroscopic signatures of 1-CNN+ and evaluate the hypothesis that this small aromatic system, stabilised by RF, may be able to survive in regions of the ISM exposed to UV photons

Infrared action spectroscopy of doubly charged PAHs and their contribution to the aromatic infrared bands

The so-called aromatic infrared bands are attributed to emission of polycyclic aromatic hydrocarbons. The observed variations toward different regions in space are believed to be caused by contributions of different classes of PAH molecules, i.e. with respect to their size, structure, and charge state. Laboratory spectra of members of these classes are needed to compare them to observations and to benchmark quantum-chemically computed spectra of these species. In this paper we present the experimental infrared spectra of three different PAH dications, naphthalene$^{2+}$, anthracene$^{2+}$, and phenanthrene$^{2+}$, in the vibrational fingerprint region 500-1700~cm$^{-1}$. The dications were produced by electron impact ionization of the vapors with 70 eV electrons, and they remained stable against dissociation and Coulomb explosion. The vibrational spectra were obtained by IR predissociation of the PAH$^{2+}$ complexed with neon in a 22-pole cryogenic ion trap setup coupled to a free-electron infrared laser at the Free-Electron Lasers for Infrared eXperiments (FELIX) Laboratory. We performed anharmonic density-functional theory calculations for both singly and doubly charged states of the three molecules. The experimental band positions showed excellent agreement with the calculated band positions of the singlet electronic ground state for all three doubly charged species, indicating its higher stability over the triplet state. The presence of several strong combination bands and additional weaker features in the recorded spectra, especially in the 10-15~$\mu$m region of the mid-IR spectrum, required anharmonic calculations to understand their effects on the total integrated intensity for the different charge states. These measurements, in tandem with theoretical calculations, will help in the identification of this specific class of doubly-charged PAHs as carriers of AIBs.Comment: Accepted for publication in A&

Top-down formation of ethylene from fragmentation of superhydrogenated polycyclic aromatic hydrocarbons

Context. Fragmentation is an important decay mechanism for polycyclic aromatic hydrocarbons (PAHs) under harsh interstellar conditions and represents a possible formation pathway for small molecules such as H2, C2H2, and C2H4. Aims. Our aim is to investigate the dissociation mechanism of superhydrogenated PAHs that undergo energetic processing and the formation pathway of small hydrocarbons. Methods. We obtain, experimentally, the mass distribution of protonated tetrahydropyrene $\left( {{{\rm{C}}_{16}}{\rm{H}}_{15}^ + ,\;{{\left[ {py + 5H} \right]}^ + }} \right)$ and protonated hex-ahydropyrene $\left( {{{\rm{C}}_{16}}{\rm{H}}_{17}^ + ,\;{{\left[ {py + 7H} \right]}^ + }} \right)$ upon collision-induced dissociation (CID). The infrared (IR) spectra of their main fragments are recorded by infrared multiple-photon dissociation (IRMPD). Extended tight-binding (GFN2-xTB) based molecular dynamics (MD) simulations were performed in order to provide the missing structure information for this experiment and to identify fragmentation path ways. The pathways for fragmentation were further investigated at a hybrid density functional theory (DFT) and dispersion-corrected level. Results. A strong signal for loss of 28 mass units of [py + 7H]+ is observed both in the CID experiment and the MD simulation, while [py + 5H]+ shows a negligible signal for the product corresponding to a mass loss of 28. The 28 mass loss from [py + 7H]+ is assigned to the loss of ethylene (C2H4) and a good fit between the calculated and experimental IR spectrum of the resulting fragment species is obtained. Further DFT calculations show favorable kinetic pathways for loss of C2H4 from hydrogenated PAH configurations involving three consecutive CH2 molecular entities. Conclusions. This joint experimental and theoretical investigation proposes a chemical pathway of ethylene formation from fragmentation of superhydrogenated PAHs. This pathway is sensitive to hydrogenated edges (e.g., the degree of hydrogenation and the hydrogenated positions). The inclusion of this pathway in astrochemical models may improve the estimated abundance of ethylene

The Sequence of Coronene Hydrogenation Revealed by Gas-phase IR Spectroscopy

The solar magnetic field (SMF) has historically been considered as dipole in order to build models of the radially expanding corona, that is, the solar wind in the solar minimum. The simplified approach suggests the existence of only one quasi-stationary current sheet (QCS) of solar origin in the heliosphere, namely, the heliospheric current sheet (HCS). However, the SMF becomes more complicated over the solar cycle, comprising higher-order components. The overlapping of the dipole and multipole components of the SMF suggests a formation of more than one QCS in the corona, which may expand further to the heliosphere. We study the impact of the.,Qquadrupole and octupole harmonics of the SMF on the formation and spatial characteristics of QCSs, building a stationary axisymmetric MHD model of QCSs in the heliosphere. It is shown that if the dipole component dominates, a single QCS appears in the solar wind at low heliolatitudes as the classic HCS. In other.,Qcases, the number of QCSs varies from one to three, depending on the relative input of the quadrupole and octupole components. QCSs possess a conic form and may occur at a wide variety of heliolatitudes. The existence of QCSs opens wide opportunities for explanations of puzzling observations of cosmic rays and energetic particles in the heliosphere and, at the same time, raises a risk of misinterpretation of in situ crossings of QCSs because of mixing up the HCS and higherheliolatitude QCSs, which can be significantly disturbed in the dynamical solar wind.</p

The Sequence of Coronene Hydrogenation Revealed by Gas-phase IR Spectroscopy

The solar magnetic field (SMF) has historically been considered as dipole in order to build models of the radially expanding corona, that is, the solar wind in the solar minimum. The simplified approach suggests the existence of only one quasi-stationary current sheet (QCS) of solar origin in the heliosphere, namely, the heliospheric current sheet (HCS). However, the SMF becomes more complicated over the solar cycle, comprising higher-order components. The overlapping of the dipole and multipole components of the SMF suggests a formation of more than one QCS in the corona, which may expand further to the heliosphere. We study the impact of the.,Qquadrupole and octupole harmonics of the SMF on the formation and spatial characteristics of QCSs, building a stationary axisymmetric MHD model of QCSs in the heliosphere. It is shown that if the dipole component dominates, a single QCS appears in the solar wind at low heliolatitudes as the classic HCS. In other.,Qcases, the number of QCSs varies from one to three, depending on the relative input of the quadrupole and octupole components. QCSs possess a conic form and may occur at a wide variety of heliolatitudes. The existence of QCSs opens wide opportunities for explanations of puzzling observations of cosmic rays and energetic particles in the heliosphere and, at the same time, raises a risk of misinterpretation of in situ crossings of QCSs because of mixing up the HCS and higherheliolatitude QCSs, which can be significantly disturbed in the dynamical solar wind.Astrodynamics & Space Mission