Infrared bands of neutral gas-phase carbon clusters in a broad spectral range.

The identification of species in the interstellar medium requires precise and molecule-specific spectroscopic information in the laboratory framework, in broad spectral ranges and under conditions relevant to interstellar environments. In this work, we measure the gas-phase infrared spectra of neutral carbon clusters, CN (N = 6-11), in a molecular beam. The CN distribution is formed by photofragmentation of C60 molecules, concurrently showing a top-down formation mechanism. A broad spectral range in the infrared between 500-3200 cm-1 (20-3.125 µm) is investigated. We observe strong bands between 5 and 6 µm, in conjunction with novel features in the 3 µm region. Density functional theory calculations reveal that these short wavelength modes correspond to combination bands with significant infrared intensity. Moreover, we identify the N ≤ 10 clusters as linear, while C11 adopts a ring configuration, placing the linear-to-ring transition at N = 11 under our molecular beam conditions. The linearity of C10 is discussed based on the formation pathway from larger clusters in energetic conditions. Given the vast and very precise infrared information already been released from the James Webb Space Telescope mission, this infrared spectroscopic data set in conjunction with information on formation mechanisms is of major relevance for identifying neutral carbon clusters in astronomical environments.

Urocanic acid as a novel scaffold for next-gen nature-inspired sunscreens: I. electronic laser spectroscopy under isolated conditions.

Urocanic acid is a naturally occurring UV-A and UV-B absorbing compound found in the skin. Its use in artificial sunscreens has been abandoned because of health risks associated with the cis isomer. Here we report laser spectroscopic studies on urocanic acid and various substituted derivatives under supersonically cooled conditions. We find that the spectroscopy and excited-state dynamics of urocanic acid are dominantly determined by the nearly degenerate 1nπ* and 1ππ* electronically excited states. These properties are only affected to a minor extent by esterification of the carboxylic acid group or NH alkylation of the N3H tautomer. Tautomerization, on the other hand, has a much more profound influence and leads-from a photoprotective point of view-to more favorable excited-state dynamics. The approach presented here paves the way to tailoring the photoactive properties of urocanic acid for specific applications amongst which their use as safe UV filters.

Ultrafast dynamics of fluorene initiated by highly intense laser fields.

We present an investigation of the ultrafast dynamics of the polycyclic aromatic hydrocarbon fluorene initiated by an intense femtosecond near-infrared laser pulse (810 nm) and probed by a weak visible pulse (405 nm). Using a multichannel detection scheme (mass spectra, electron and ion velocity-map imaging), we provide a full disentanglement of the complex dynamics of the vibronically excited parent molecule, its excited ionic states, and fragments. We observed various channels resulting from the strong-field ionization regime. In particular, we observed the formation of the unstable tetracation of fluorene, above-threshold ionization features in the photoelectron spectra, and evidence of ubiquitous secondary fragmentation. We produced a global fit of all observed time-dependent photoelectron and photoion channels. This global fit includes four parent ions extracted from the mass spectra, 15 kinetic-energy-resolved ionic fragments extracted from ion velocity map imaging, and five photoelectron channels obtained from electron velocity map imaging. The fit allowed for the extraction of 60 lifetimes of various metastable photoinduced intermediates.

IR/UV Double Resonance Study of the 2-Phenylallyl Radical and its Pyrolysis Products.

Isolated 2-phenylallyl radicals (2-PA), generated by pyrolysis from a nitrite precursor, have been investigated by IR/UV ion dip spectroscopy using free electron laser radiation. 2-PA is a resonance-stabilized radical that is considered to be involved in the formation of polycyclic aromatic hydrocarbons (PAH) in combustion, but also in interstellar space. The radical is identified based on its gas-phase IR spectrum. Furthermore, a number of bimolecular reaction products are identified, showing that the self-reaction as well as reactions with unimolecular decomposition products of 2-PA form several PAH efficiently. Possible mechanisms are discussed and the chemistry of 2-PA is compared with the one of the related 2-methylallyl and phenylpropargyl radicals.

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.

The gas-phase infrared spectra of the 2-methylallyl radical and its high-temperature reaction products.

The resonance-stabilized 2-methylallyl radical, 2-MA, is considered as a possible intermediate in the formation of polycyclic aromatic hydrocarbons (PAHs) in combustion processes. In this work, we report on its contribution to molecular growth in a high-temperature microreactor and provide mass-selective IR/UV ion dip spectra of the radical, as well as the various jet-cooled reaction products, employing free electron laser radiation in the mid-infrared region. Small (aromatic) hydrocarbons such as fulvene, benzene, styrene, or para-xylene, as well as polycyclic molecules, like (methylated) naphthalene, were identified with the aid of ab initio DFT computations. Several reaction products differ by one or more methyl groups, suggesting that molecular growth is dominated by (de)methylation in the reactor.

Polycyclic aromatic hydrocarbon growth in a benzene discharge explored by IR-UV action spectroscopy.

Infrared signatures of polycyclic aromatic hydrocarbons (PAHs) are detected towards many phases of stellar evolution. PAHs are major players in the carbon chemistry of the interstellar medium, forming the connection between small hydrocarbons and large fullerenes. However, as details on the formation of PAHs in these environments are still unclear, modeling their abundance and chemistry has remained far from trivial. By combining molecular beam mass-selective IR spectroscopy and calculated IR spectra, we analyze the discharge of benzene and identify resulting products including larger PAHs, radicals and intermediates that serve as promising candidates for radio astronomical searches. The identification of various reaction products indicates that different gas-phase reaction mechanisms leading to PAH growth must occur under the same conditions to account for all observed PAH-related species, thereby revealing the complex and interconnected network of PAH formation pathways. The results of this study highlight key (exothermic) reactions that need to be included in astrochemical models describing the carbon chemistry in our universe.

The kinetic energy of PAH dication and trication dissociation determined by recoil-frame covariance map imaging.

We investigated the dissociation of dications and trications of three polycyclic aromatic hydrocarbons (PAHs), fluorene, phenanthrene, and pyrene. PAHs are a family of molecules ubiquitous in space and involved in much of the chemistry of the interstellar medium. In our experiments, ions are formed by interaction with 30.3 nm extreme ultraviolet (XUV) photons, and their velocity map images are recorded using a PImMS2 multi-mass imaging sensor. Application of recoil-frame covariance analysis allows the total kinetic energy release (TKER) associated with multiple fragmentation channels to be determined to high precision, ranging 1.94-2.60 eV and 2.95-5.29 eV for the dications and trications, respectively. Experimental measurements are supported by Born-Oppenheimer molecular dynamics (BOMD) simulations.

Far-IR and UV spectral signatures of controlled complexation and microhydration of the polycyclic aromatic hydrocarbon acenaphthene.

In this work we report on the experimental and theoretical investigations of the progressional complexation of the polycyclic aromatic hydrocarbon (PAH) acenaphthene with itself and with water. In the interstellar medium, PAH complexes are an important link between molecular gas and solid state configurations of carbon, and in the form of grains they are postulated to serve as chemical catalysts. However, no direct detection of PAHs or their (microhydrated) complexes in interstellar space has been achieved as of yet. Therefore, we provide UV and far-infrared ion dip spectra of homogeneous PAH multimers and their hydrated clusters. The far-IR region of the IR spectrum is especially interesting since it contains the most spectral features that arise due to complexation or microhydration. We present microhydrated PAH complexes up to the third order, where we show that the water clusters are locked with little perturbation on the different PAH platforms. Density functional theory (DFT) calculations involving hydrogen bond interactions still seem challenging for predicting the far-IR frequency range, although applying anharmonic corrections leads to slight improvements.

Interfacial Nanostructure and Hydrogen Bond Networks of Choline Chloride and Glycerol Mixtures Probed with X-ray and Vibrational Spectroscopies.

The molecular distribution at the liquid-vapor interface and evolution of the hydrogen bond interactions in mixtures of glycerol and choline chloride are investigated using X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Nanoscale depth profiles of supersaturated deep eutectic solvent (DES) mixtures up to ∼2 nm measured by ambient-pressure XPS show the enhancement of choline cation (Ch+) concentration by a factor of 2 at the liquid-vapor interface compared to the bulk. In addition, Raman spectral analysis of a wide range of DES mixtures reveals the conversion of gauche-conformer Ch+ into the anti-conformer in relatively lower ChCl concentrations. Finally, the depletion of Ch+ from the interface (probing depth = 0.4 nm) is demonstrated by aerosol-based velocity map imaging XPS measurements of glyceline and water mixtures. The nanostructure of liquid-vapor interfaces and structural rearrangement by hydration can provide critical insight into the molecular origin of the deep eutectic behavior and gas-capturing application of DESs.

Wetting of a Hydrophobic Surface: Far-IR Action Spectroscopy and Dynamics of Microhydrated Naphthalene.

The interaction of water and polycyclic aromatic hydrocarbons is of fundamental importance in areas as diverse as materials science and atmospheric and interstellar chemistry. The interplay between hydrogen bonding and dipole-π interactions results in subtle dynamics that are challenging to describe from first principles. Here, we employ far-IR action vibrational spectroscopy with the infrared free-electron laser FELIX to investigate naphthalene with one to three water molecules. We observe diffuse bands associated with intermolecular vibrational modes that serve as direct probes of the loose binding of water to the naphthalene surface. These signatures are poorly reproduced by static DFT or Møller-Plesset computations. Instead, a rationalization is achieved through Born-Oppenheimer Molecular Dynamics simulations, revealing the active mobility of water over the surface, even at low temperatures. Therefore, our work provides direct insights into the wetting interactions associated with shallow potential energy surfaces while simultaneously demonstrating a solid experimental-computational framework for their investigation.

Stacking Is Favored over Hydrogen Bonding in Azaphenanthrene Dimers.

N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.

Polycyclic aromatic hydrocarbon formation chemistry in a plasma jet revealed by IR-UV action spectroscopy.

Large polycyclic aromatic hydrocarbons (PAHs) are the most abundant complex molecules in the interstellar medium; however, their possible formation pathways from small molecular species are still elusive. In the present work, we follow and characterize the formation of PAHs in an electrical discharge, specifically the PAH naphthalene in a molecular beam of argon. The fragments, products and reaction intermediates are unambiguously structurally identified by mass-selective IR-UV spectroscopy combined with quantum chemical calculations. This experiment provides evidence of the formation of larger PAHs containing up to four cyclic rings in the gas phase originating from a non-radical PAH molecule as a precursor. In addition to PAH formation, key resonance stabilized radical intermediates and intermediates containing di-acetylenic side groups are unambiguously identified in our experiment. We thereby not only reveal competing formation pathways to larger PAHs, but also identify intermediate species to PAH formation that are candidates for detection in radio-astronomy.

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.