Photofragmentation of corannulene (C20H10) and sumanene (C21H12) cations in the gas phase and their astrophysical implications.

Aromatic infrared bands (AIBs) dominate the mid-infrared spectra of many galactic and extragalactic sources. These AIBs are generally attributed to fluorescence emission from aromatic molecules. Unified efforts from experimentalists and theoreticians to assign these AIB features have recently received additional impetus with the launch of the James Webb Space Telescope (JWST) as the Mid-InfraRed Instrument (MIRI) delivers a mid-IR spectrum with greatly increased sensitivity and spectral resolution. PAHs in space can exist in either neutral or ionic form, absorb UV photons and undergo fragmentation, becoming a rich source of small hydrocarbons. This top-down mechanism of larger PAHs fragmenting into smaller species is of utmost importance in photo-dissociation regions (PDR) in space. In this work, we experimentally and theoretically investigate the photo-fragmentation pathways of two astronomically significant PAH cations - corannulene (C20H10) and sumanene (C21H12), which are structural motifs of fullerene C60, to understand their sequential fragmentation pathways. The photo-fragmentation experiments exhibit channels that are significantly different from planar PAHs. The breakdown of the carbon skeleton is found to follow different pathways for C20H10 and C21H12 because of the number and positioning of pentagon rings, yet the most abundant low mass cations produced by these two species are found to be similar. The low mass cations showcased in this work could be of interest due to their possible astronomical detections. For completeness, the qualitative photofragmentation behaviour of dicationic corannulene and sumanene has also been investigated, but the potential energy surface of these dications is beyond the scope of this paper.

Laser-induced fragmentation of coronene cations.

Polycyclic aromatic hydrocarbons are an important component of the interstellar medium of galaxies and photochemistry plays a key role in the evolution of these species in space. Here, we explore the photofragmentation behaviour of the coronene cation (C24H12˙+) using time-of-flight mass spectrometry. The experiments show photodissociation fragmentation channels including the formation of bare carbon clusters (Cn˙+) and hydrocarbon chains (CnHx+). The mass spectrum of coronene is dominated by peaks from C11˙+ and C7H+. Density functional theory was used to calculate relative energies, potential dissociation pathways, and possible structures for relevant species. We identify 6-6 → 5-7 ring isomerisation as a key step in the formation of both the bare carbon clusters and the hydrocarbon chains observed in this study. We present the dissociation mechanism outlined here as a potential formation route for C60 and other astrochemically relevant species.

The infrared absorption spectrum of phenylacetylene and its deuterated isotopologue in the mid- to far-IR.

Anharmonicity strongly influences the absorption and emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules. Here, IR-UV ion-dip spectroscopy experiments together with detailed anharmonic computations reveal the presence of fundamental, overtone, as well as 2- and 3-quanta combination band transitions in the far- and mid-infrared absorption spectra of phenylacetylene and its singly deuterated isotopologue. Strong absorption features in the 400-900 cm-1 range originate from CH(D) in-plane and out-of-plane wags and bends, as well as bending motions including the C≡C and CH bonds of the acetylene substituent and the aromatic ring. For phenylacetylene, every absorption feature is assigned either directly or indirectly to a single or multiple vibrational mode(s). The measured spectrum is dense, broad, and structureless in many regions but well characterized by computations. Upon deuteration, large isotopic shifts are observed. At frequencies above 1500 cm-1 for d1-phenylacetylene, a one-to-one match is seen when comparing computations and experiments with all features assigned to combination bands and overtones. The C≡C stretch observed in phenylacetylene is not observed in d1-phenylacetylene due to a computed 40-fold drop in intensity. Overall, a careful treatment of anharmonicity that includes 2- and 3-quanta modes is found to be crucial to understand the rich details of the infrared spectrum of phenylacetylene. Based on these results, it can be expected that such an all-inclusive anharmonic treatment will also be key for unraveling the infrared spectra of PAHs in general.

A far-ultraviolet-driven photoevaporation flow observed in a protoplanetary disk.

Most low-mass stars form in stellar clusters that also contain massive stars, which are sources of far-ultraviolet (FUV) radiation. Theoretical models predict that this FUV radiation produces photodissociation regions (PDRs) on the surfaces of protoplanetary disks around low-mass stars, which affects planet formation within the disks. We report James Webb Space Telescope and Atacama Large Millimeter Array observations of a FUV-irradiated protoplanetary disk in the Orion Nebula. Emission lines are detected from the PDR; modeling their kinematics and excitation allowed us to constrain the physical conditions within the gas. We quantified the mass-loss rate induced by the FUV irradiation and found that it is sufficient to remove gas from the disk in less than a million years. This is rapid enough to affect giant planet formation in the disk.

Size distribution of polycyclic aromatic hydrocarbons in space: an old new light on the 11.2/3.3 µm intensity ratio.

The intensity ratio of the 11.2/3.3 µm emission bands is considered to be a reliable tracer of the size distribution of polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM). This paper describes the validation of the calculated intrinsic infrared (IR) spectra of PAHs that underlie the interpretation of the observed ratio. The comparison of harmonic calculations from the NASA Ames PAH IR spectroscopic database to gas-phase experimental absorption IR spectra reveals a consistent underestimation of the 11.2/3.3 µm intensity ratio by 34%. IR spectra based on higher level anharmonic calculations, on the other hand, are in very good agreement with the experiments. While there are indications that the 11.2/3.3 µm ratio increases systematically for PAHs in the relevant size range when using a larger basis set, it is unfortunately not yet possible to reliably calculate anharmonic spectra for large PAHs. Based on these considerations, we have adjusted the intrinsic ratio of these modes and incorporated this in an interstellar PAH emission model. This corrected model implies that typical PAH sizes in reflection nebulae such as NGC 7023 - previously inferred to be in the range of 50 to 70 carbon atoms per PAH are actually in the range of 40 to 55 carbon atoms. The higher limit of this range is close to the size of the C60 fullerene (also detected in reflection nebulae), which would be in line with the hypothesis that, under appropriate conditions, large PAHs are converted into the more stable fullerenes in the ISM.

Adsorption of Polycyclic Aromatic Hydrocarbons and C60 onto Forsterite: C-H Bond Activation by the Schottky Vacancy.

Understanding how to catalytically break the C-H bond of aromatic molecules, such as polycyclic aromatic hydrocarbons (PAHs), is currently a big challenge and a subject of study in catalysis, astrochemistry, and planetary science. In the latter, the study of the breakdown reaction of PAHs on mineral surfaces is important to understand if PAHs are linked to prebiotic molecules in regions of star and planet formation. In this work, we employed a periodic density functional theory along with Grimme's D4 (DFT-D4) approach for studying the adsorption of a sample of PAHs (naphthalene, anthracene, fluoranthene, pyrene, coronene, and benzocoronene) and fullerene on the [010] forsterite surface and its defective surfaces (Fe-doped and Ni-doped surfaces and a MgO-Schottky vacancy) for their implications in catalysis and astrochemistry. On the basis of structural and binding energy analysis, large PAHs and fullerene present stronger adsorption on the pristine, Fe-doped, and Ni-doped forsterite surfaces than small PAHs. On a MgO-Schottky vacancy, parallel adsorption of the PAH leads to the chemisorption process (C-Si and/or C-O bonds), whereas perpendicular orientation of the PAH leads to the catalytic breaking of the aromatic C-H bond via a barrierless reaction. Spin density and charge analysis show that C-H dissociation is promoted by electron donation from the vacancy to the PAH. As a result of the undercoordinated Si and O atoms, the vacancy acts as a Frustrated Lewis Pair (FLP) catalyst. Therefore, a MgO-Schottky vacancy [010] forsterite surface proved to have potential catalytic activity for the activation of C-H bond in aromatic molecules.

Anharmonicity and the IR Emission Spectrum of Neutral Interstellar PAH Molecules.

The characteristics of the CH stretching and out-of-plane bending modes in polycyclic aromatic hydrocarbon molecules are investigated using anharmonic density functional theory (DFT) coupled to a vibrational second-order perturbation treatment taking resonance effects into account. The results are used to calculate the infrared emission spectrum of vibrationally excited species in the collision-less environment of interstellar space. This model follows the energy cascade as the molecules relax after the absorption of a UV photon in order to calculate the detailed profiles of the infrared bands. The results are validated against elegant laboratory spectra of polycyclic aromatic hydrocarbon absorption and emission spectra obtained in molecular beams. The factors which influence the peak position, spectral detail, and relative strength of the CH stretching and out-of-plane bending modes are investigated, and detailed profiles for these modes are derived. These are compared to observations of astronomical objects in space, and the implications for our understanding of the characteristics of the molecular inventory of space are assessed.

Experimental and Theoretical Constraints on Amino Acid Formation from PAHs in Asteroidal Settings.

Amino acids and polycyclic aromatic hydrocarbons (PAHs) belong to the range of organic compounds detected in meteorites. In this study, we tested empirically and theoretically if PAHs are precursors for amino acids in carbonaceous chondrites, as previously suggested. We conducted experiments to synthesize amino acids from fluoranthene (PAH), with ammonium bicarbonate as a source for ammonia and carbon dioxide under mimicked asteroidal conditions. In our thermodynamic calculations, we extended our analysis to additional PAH-amino acid combinations. We explored 36 reactions involving the PAHs naphthalene, anthracene, fluoranthene, pyrene, triphenylene, and coronene and the amino acids glycine, alanine, valine, leucine, phenylalanine, and tyrosine. Our experiments do not show the formation of amino acids, whereas our theoretical results hint that PAHs could be precursors of amino acids in carbonaceous chondrites at low temperatures.

Modeling the infrared cascade spectra of small PAHs: the 11.2 µm band.

The profile of the 11.2 µm feature of the infrared (IR) cascade emission spectra of polycyclic aromatic hydrocarbon (PAH) molecules is investigated using a vibrational anharmonic method. Several factors are found to affect the profile including: the energy of the initially absorbed ultraviolet (UV) photon, the density of vibrational states, the anharmonic nature of the vibrational modes, the relative intensities of the vibrational modes, the rotational temperature of the molecule, and blending with nearby features. Each of these factors is explored independently and influence either the red or blue wing of the 11.2 µm feature. The majority impact solely the red wing, with the only factor altering the blue wing being the rotational temperature.

Stellar feedback and triggered star formation in the prototypical bubble RCW 120.

Radiative and mechanical feedback of massive stars regulates star formation and galaxy evolution. Positive feedback triggers the creation of new stars by collecting dense shells of gas, while negative feedback disrupts star formation by shredding molecular clouds. Although key to understanding star formation, their relative importance is unknown. Here, we report velocity-resolved observations from the SOFIA (Stratospheric Observatory for Infrared Astronomy) legacy program FEEDBACK of the massive star-forming region RCW 120 in the [CII] 1.9-THz fine-structure line, revealing a gas shell expanding at 15 km/s. Complementary APEX (Atacama Pathfinder Experiment) CO J = 3-2 345-GHz observations exhibit a ring structure of molecular gas, fragmented into clumps that are actively forming stars. Our observations demonstrate that triggered star formation can occur on much shorter time scales than hitherto thought (<0.15 million years), suggesting that positive feedback operates on short time periods.

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method.

Density functional theory (DFT) has provided deep atomic-level insights into the adsorption behavior of aromatic molecules on solid surfaces. However, modeling the surface phenomena of large molecules on mineral surfaces with accurate plane wave methods (PW) can be orders of magnitude more computationally expensive than localized atomic orbitals (LCAO) methods. In the present work, we propose a less costly approach based on the DFT-D4 method (PBE-D4), using LCAO, to study the interactions of aromatic molecules with the {010} forsterite (Mg2SiO4) surface for their relevance in astrochemistry. We studied the interaction of benzene with the pristine {010} forsterite surface and with transition-metal cations (Fe2+ and Ni2+) using PBE-D4 and a vdW-inclusive density functional (Dion, Rydberg, Schröder, Langreth, and Lundqvist (DRSLL)) with LCAO methods. PBE-D4 shows good agreement with coupled-cluster methods (CCSD(T)) for the binding energy trend of cation complexes and with PW methods for the binding energy of benzene on the forsterite surface with a difference of about 0.03 eV. The basis set superposition error (BSSE) correction is shown to be essential to ensure a correct estimation of the binding energies even when large basis sets are employed for single-point calculations of the optimized structures with smaller basis sets. We also studied the interaction of naphthalene and benzocoronene on pristine and transition-metal-doped {010} forsterite surfaces as a test case for PBE-D4. Yielding results that are in good agreement with the plane wave methods with a difference of about 0.02-0.17 eV, the PBE-D4 method is demonstrated to be effective in unraveling the binding structures and the energetic trends of aromatic molecules on pristine and transition-metal-doped forsterite mineral surfaces. Furthermore, PBE-D4 results are in good agreement with its predecessor PBE-D3(BJM) and with the vdW-inclusive density functionals, as long as transition metals are not involved. Hence, PBE-D4/CP-DZP has been proven to be a robust theory level to study the interaction of aromatic molecules on mineral surfaces.

A Spectroscopic View on Cosmic PAH Emission.

ConspectusPolycyclic aromatic hydrocarbon molecules (PAHs) are ubiquitously present at high abundances in the Universe. They are detected through their infrared (IR) fluorescence UV pumped by nearby massive stars. Hence, their infrared emission is used to determine the star formation rate in galaxies, one of the key indicators for understanding the evolution of galaxies. Together with fullerenes, PAHs are the largest molecules found in space. They significantly partake in a variety of physical and chemical processes in space, influencing star and planet formation as well as galaxy evolution.Since the IR features from PAHs originate from chemical bonds involving only nearest neighbor atoms, they have only a weak dependence on the size and structure of the molecule, and it is therefore not possible to identify the individual PAH molecules that make up the cosmic PAH family. This strongly hampers the interpretation of their astronomical fingerprints. Despite the lack of identification, constraints can be set on the characteristics of the cosmic PAH family thanks to a joint effort of astronomers, physicists, and chemists.This Account presents the spectroscopic properties of the cosmic PAH emission as well as the intrinsic spectroscopic properties of PAHs and astronomical modeling of the PAH evolution required for the interpretation of the cosmic PAH characteristics. We discuss the observed spectral signatures tracing PAH properties such as charge, size, and structure and highlight the related challenges. We discuss the recent success of anharmonic calculations of PAH infrared absorption and emission spectra and outline the path forward. Finally, we illustrate the importance of models on PAH processing for the interpretation of the astronomical data in terms of the charge balance and PAH destruction.Throughout this Account, we emphasize that huge progress is on the horizon on the astronomical front. Indeed, the world is eagerly awaiting the launch of the James Webb Space Telescope (JWST). With its incredible improvement in spatial resolution, combined with its complete spectral coverage of the PAH infrared emission bands at medium spectral resolution and superb sensitivity, the JWST will revolutionize PAH research. Previous observations could only present spectra averaged over regions with vastly different properties, thus greatly confusing their interpretation. The amazing spatial resolution of JWST will disentangle these different regions. This will allow us to quantify precisely how PAHs are modified by the physical conditions of their host environment and thus trace how PAHs evolve across space. However, this will only be achieved when the necessary (and still missing) fundamental properties of PAHs, outlined in this Account, are known. We strongly encourage you to join this effort.

IR photofragmentation of the phenyl cation: spectroscopy and fragmentation pathways.

We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio (C6H5+) and perdeutero (C6D5+) forms, in the 260-1925 cm-1 (5.2-38 µm) spectral range, and investigate the observed photofragmentation. The spectral and fragmentation data were obtained using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy within a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR MS) located inside the cavity of the free electron laser FELICE (Free Electron Laser for Intra-Cavity Experiments). The 1A1 singlet nature of the phenylium ion is ascertained by comparison of the observed IR spectrum with DFT calculations, using both harmonic and anharmonic frequency calculations. To investigate the observed loss of predominantly [2C,nH] (n = 2-4) fragments, we explored the potential energy surface (PES) to unravel possible isomerization and fragmentation reaction pathways. The lowest energy pathways toward fragmentation include direct H elimination, and a combination of facile ring-opening mechanisms (≤2.4 eV), followed by elimination of H or CCH2. Energetically, all H-loss channels found are more easily accessible than CCH2-loss. Calculations of the vibrational density of states for the various intermediates show that at high internal energies, ring opening is thermodynamically the most advantageous, eliminating direct H-loss as a competing process. The observed loss of primarily [2C,2H] can be explained through entropy calculations that show favored loss of [2C,2H] at higher internal energies.

Far-IR Absorption of Neutral Polycyclic Aromatic Hydrocarbons (PAHs): Light on the Mechanism of IR-UV Ion Dip Spectroscopy.

Gas-phase IR-UV double-resonance laser spectroscopy is an IR absorption technique that bridges the gap between experimental IR spectroscopy and theory. The IR experiments are used to directly evaluate predicted frequencies and potential energy surfaces as well as to probe the structure of isolated molecules. However, a detailed understanding of the underlying mechanisms is, especially in the far-IR regime, still far from complete, even though this is crucial for properly interpreting the recorded IR absorption spectra. Here, events occurring upon excitation to vibrational levels of polycyclic aromatic hydrocarbons by far-IR radiation from the FELIX free electron laser are followed using resonance-enhanced multiphoton ionization spectroscopy. These studies provide detailed insight into how ladder climbing and anharmonicity influence IR-UV spectroscopy and therefore the resulting IR signatures in the far-IR region. Moreover, the potential energy surfaces of these low-frequency delocalized modes are investigated and shown to have a strong harmonic character.

Structural investigation of doubly-dehydrogenated pyrene cations.

The vibrationally resolved spectra of the pyrene cation and doubly-dehydrogenated pyrene cation (C16H10˙+; Py+ and C16H8˙+; ddPy+) are presented. Infrared predissociation spectroscopy is employed to measure the vibrational spectrum of both species using a cryogenically cooled 22-pole ion trap. The spectrum of Py+ allows a detailed comparison with harmonic and anharmonic density functional theory (DFT) calculated normal mode frequencies. The spectrum of ddPy+ is dominated by absorption features from two isomers (4,5-ddPy+ and 1,2-ddPy+) with, at most, minor contributions from other isomers. These findings can be extended to explore the release of hydrogen from interstellar PAH species. Our results suggest that this process favours the loss of adjacent hydrogen atoms.

Superhydrogenation of pentacene: the reactivity of zigzag-edges.

Investigating the hydrogenation of carbonaceous materials is of interest in a wide range of research areas including electronic device development, hydrogen storage, and, in particular, astrocatalytic formation of molecular hydrogen in the universe. Polycyclic Aromatic Hydrocarbons (PAHs) are ubiquitous in space, locking up close to 15% of the elementary carbon. We have used thermal desorption measurements to study the hydrogenation sequence of pentacene from adding one additional H to the fully hydrogenated pentacene species. The experiments reveal that hydrogenated species with an even number of excess H atoms are highly preferred over hydrogenated species with an odd number of H atoms. In addition, the experiments show that specific hydrogenation states of pentacene with 2, 4, 6, 10, 16 and 22 extra H atoms are preferred over other even numbers. We have investigated the structural stability and activation energy barriers for the superhydrogenation of pentacene using Density Functional Theory. The results reveal a preferential hydrogenation pattern set by the activation energy barriers of the hydrogenation steps. Based on these studies, we formulate simple concepts governing the hydrogenation that apply equally well for different PAHs.

Fully anharmonic infrared cascade spectra of polycyclic aromatic hydrocarbons.

The infrared (IR) emission of polycyclic aromatic hydrocarbons (PAHs) permeates our universe; astronomers have detected the IR signatures of PAHs around many interstellar objects. The IR emission of interstellar PAHs differs from their emission as seen under conditions on Earth as they emit through a collisionless cascade down through their excited vibrational states from high internal energies. The difficulty in reproducing interstellar conditions in the laboratory results in a reliance on theoretical techniques. However, the size and complexity of PAHs require careful consideration when producing the theoretical spectra. In this work, we outline the theoretical methods necessary to lead to fully theoretical IR cascade spectra of PAHs including: an anharmonic second order vibrational perturbation theory treatment, the inclusion of Fermi resonances through polyads, and the calculation of anharmonic temperature band shifts and broadenings (including resonances) through a Wang-Landau approach. We also suggest a simplified scheme to calculate vibrational emission spectra that retain the essential characteristics of the full IR cascade treatment and can directly transform low temperature absorption spectra in IR cascade spectra. Additionally we show that past astronomical models were in error in assuming a 15 cm-1 correction was needed to account for anharmonic emission effects.

The anharmonic quartic force field infrared spectra of hydrogenated and methylated PAHs.

Polycyclic aromatic hydrocarbons (PAHs) have been shown to be ubiquitous in a large variety of distinct astrophysical environments and are therefore of great interest to astronomers. The majority of these findings are based on theoretically predicted spectra, which make use of scaled DFT harmonic frequencies for band positions and the double harmonic approximation for intensities. However, these approximations have been shown to fail at predicting high-resolution gas-phase infrared spectra accurately, especially in the CH-stretching region (2950-3150 cm-1, 3 µm). This is particularly worrying for the subset of hydrogenated or methylated PAHs to which astronomers attribute the observed non-aromatic features that appear in the CH-stretching region of spectral observations of the interstellar medium (ISM). In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs and five non-linear PAHs, demonstrating the importance of including anharmonicities into theoretical calculations. In this work we extend these techniques to two methylated PAHs (9-methylanthracene, and 9,10-dimethylanthracene) and four hydrogenated PAHs (9,10-dihydroanthracene, 9,10-dihydrophenanthrene, 1,2,3,4-tetrahydronaphthalene, and 1,2,3,6,7,8-hexahydropyrene) in order to better understand the aliphatic IR features of substituted PAHs. The theoretical spectra are compared with the spectra obtained under matrix isolation low-temperature conditions for the full vibrational fundamental range and under high-resolution, low-temperature gas-phase conditions for the CH-stretching region. Excellent agreement is observed between the theoretical and high-resolution experimental spectra with a deviation of 0.00% ± 0.17%, and changes to the spectra of PAHs upon methylation and hydrogenated are tracked accurately and explained.

In Situ Nanoscale Investigation of Step Retreat on Fluoranthene Crystal Surfaces.

Fluoranthene, a polycyclic aromatic hydrocarbon, has been detected on Earth as well as in asteroids and meteorites and may have played a role in the formation of life. Increasing the ionic strength of aqueous solutions has been observed to lower the fluoranthene solubility, but it is unclear how solution composition controls the release rate of fluoranthene to an aqueous solution. To elucidate this, we performed in situ atomic force microscopy experiments in which we characterized the sublimation and dissolution behavior of fluoranthene crystal surfaces. From this, we quantify the step retreat rate upon exposure to air, deionized water, and a 0.4 M NaCl or 0.1 M MgSO4 solution. Surface roughness is the main factor that determines the dissolution or sublimation rate. The results imply that during fluoranthene remediation or breakdown in meteorites and asteroids, ionic strength will be more important than chemical composition for controlling fluoranthene release into solution.

Dissociative ionisation of adamantane: a combined theoretical and experimental study.

Diamond nanoparticles, or nanodiamonds, are intriguing carbon-based materials which, maybe surprisingly, are the most abundant constituent of presolar grains. While the spectroscopic properties of even quite large diamondoids have already been explored, little is known about their unimolecular fragmentation processes. In this paper we characterise the dissociative ionisation of adamantane (C10H16) - the smallest member of the diamondoid family - utilising imaging Photoelectron Photoion Coincidence (iPEPICO) spectroscopy and Density Functional Theory (DFT) calculations. We have found adamantane to dissociatively photoionise via several parallel channels of which H, C3H7 and C4H8 losses are the most important ones. Calculations confirm the existence of a rate-limiting transition state for the multiple C-loss channels, which is located at 10.55 eV with respect to neutral adamantane. In addition, we found dissociation channels leading to small cationic hydrocarbons, which may be relevant in the interstellar medium.