Compact Polycyclic Aromatic Hydrocarbons Research Articles

Fluorescence Excitation and Dispersed Fluorescence Spectra of the First Electronic Excited (S1) State of peri-Hexabenzocoronene (C42H18) Isolated in Solid para-Hydrogen.

Large polycyclic aromatic hydrocarbons (PAH) and their cationic, hydrogenated, and protonated derivatives have long been considered as promising candidates for the carriers of the diffuse interstellar bands. peri-Hexabenzocoronene (peri-HBC, C42H18) is a large, compact PAH, and, to the best of our knowledge, the largest centrosymmetric all-benzenoid PAH for which electronic spectroscopy data has been published. In this work, we present the dispersed fluorescence and fluorescence excitation spectra of the first electronic excited (S1) state of peri-HBC isolated in solid para-H2 and provide the first detailed vibronic analysis of observed features. The observed spectra agree with the emission and absorption spectra simulated according to optimized geometries and scaled harmonic vibrational frequencies calculated at the density functional theory (DFT) level using a Franck-Condon Herzberg-Teller approach; the spectral bands are associated solely with vibrational normal modes of approximate e2g symmetry and their combinations with vibrational modes of approximately a1g symmetry. We clearly observed the position of the S1-S0 electronic transition origin of peri-HBC at 22,088 cm-1 (452.7 nm), which was unreported previously. The matrix shift of ∼110 cm-1 to the red relative to the gas-phase value was estimated by comparison of two reported gas-phase bands with our work. Because of the significant deviation from the reported wavelengths of DIB, the weakness of the S1-S0 electronic transitions, and the lack of reported DIB at <400 nm where the intense S4 ← S0 band of peri-HBC is located, peri-HBC is unlikely to contribute to DIB.

Analysis of the 3.2–3.3 μm Interstellar Absorption Feature on Three Milky Way Sightlines

We report new analyses of spectra of the 3.2–3.3 μm absorption feature observed in the diffuse interstellar medium toward three Milky Way sources: 2MASS J17470898 − 2829561 (2M1747) and the Quintuplet Cluster, both located in the Galactic center, and Cygnus OB2-12. The 3.2–3.3 μm interval coincides with the CH-stretching region for compact polycyclic aromatic hydrocarbons (PAHs). We focus on the 2M1747 spectrum. Its published optical depth spectrum contains residual telluric transmission features, which arise from the 0.06 difference in mean airmasses between the observations of the source and its telluric standard star. We corrected the published spectrum by adding the airmass residual optical depth spectrum. The corrected spectrum is well fit by a superposition of four Gaussians. The absorption spectra of the other two sources were also fit by four Gaussians, with similar central wavelengths, widths, and relative peak opacities. We associate the three longer wavelength Gaussians covering the 3.23–3.31 μm interval with compact PAHs in positive, neutral, and negative charge states. We identify the shortest-wavelength Gaussian, near 3.21 μm, with irregularly shaped PAHs. Constraints imposed by spectral smoothness on the corrected 2M1747 spectrum, augmented by a PAH cluster formation model for post-asymptotic giant branch stars, suggests that >99% of the PAHs in the diffuse interstellar medium reside in small clusters. This study supports the PAH hypothesis, and it suggests that a family of primarily compact PAHs with a C66H20 (circumvalene) parent is consistent with the observed mid-infrared and ultraviolet interstellar absorption spectrum.

Study of vibrational spectra of polycyclic aromatic hydrocarbons with phenyl side group

Computational study of polycyclic aromatic hydrocarbons (PAHs) with phenyl side group substituted at different positions is reported. The infrared spectral variations due to the position of phenyl substitution, ionization state and the size of the molecules are discussed and possible contribution of phenyl-PAHs to the mid-infrared emission features from astrophysical objects is analysed. Structurally phenyl group substitution at 2nd position gives more stable species compared to substitution at other positions. Phenyl-PAHs exhibit new aromatic bands near 695 and 741 cm−1 (14.4 and 13.5μm), due to contribution from quintet CH wag, that compare well with minor features at 14.2 and 13.5μm observed in several astrophysical objects. Just as in plain PAHs, the C–C stretch vibrational modes (∼1600 cm−1) have negligible intensity in neutrals, but the cations of all phenyl-PAHs exhibit significantly strong phenyl group C–C stretch peak close to class B type 6.2μm astrophysical band. In 2-phenylpyrene, it is the neutral molecule that exhibits this strong feature in the 6.2μm range along with other features that match with sub-features at 6.66 and 6.9μm, observed in astronomical spectra of some late type objects. The substitution of phenyl side group at solo position shifts the C–C stretch mode of parent PAH close to the region of 6.2μm astrophysical band. The results indicate possibility of phenyl-PAHs in space and the bottom-up formation of medium sized compact PAHs with phenyl side group in carbon rich cool circumstellar shells. Phenyl-PAHs need to be considered in modelling mid-infrared emission spectra of various astrophysical objects.

Molecular clusters played an important role in the adsorption of polycyclic aromatic hydrocarbons (PAHs) on carbonaceous materials

Polycyclic aromatic hydrocarbons (PAHs) are one of the most frequently detected hydrophobic organic contaminants (HOCs) in the environment. They may form clusters because of the strong hydrophobic and π-π electron-donor-acceptor (EDA) interactions among PAHs molecules. However, previous experimental studies and theoretical simulations generally ignored the impact of molecular clusters on the adsorption, which may result in the misunderstanding of the environmental fate and risk. In this work, naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) were selected to investigate intermolecular interaction as well as the consequent impact on their adsorption on graphene. The density field of C atoms in equilibrium configurations of self-interacted PAHs suggested that the formation of PAHs molecular clusters was a spontaneous process, and was favored in solvents with stronger polarity and for PAHs with more benzene rings. It should be noted that the molecular dynamics simulations with the initial state of molecular clusters matched better with the published experimental results compared with those of individual PAHs. The formed compact PAHs clusters in polar solvents increased the apparent PAHs adsorption, because of their higher hydrophobic and π-π EDA interactions. This study emphasized that the self-interaction of PAHs should be carefully considered in both experimental and theoretical simulation studies.

A comparative multi-state multi-dimensional quantum-classical dynamics on compact polycyclic aromatic hydrocarbons (CPAHs) by parallel TDDVR method

The newly implemented parallelized quantum–classical dynamical approach, namely, Time Dependent Discrete Variable Representation (TDDVR) method is applied to the spectroscopically important phenanthrene, acenaphthene and pyrene, where several conical intersections exist in their four lowest singlet excited electronic states (X, A, B and C), to illustrate their various dynamical aspects. This parallel version shows almost linear scalability with increasing number of computing processors. First principles dynamics is performed to the adopted Hamiltonians to obtain photoelectron (PE) spectra, zero electron kinetic energy (ZEKE) spectra, population dynamics and many other dynamical observables. The reduced densities of the wave packet (WP) in coupled electronic surfaces are used to elucidate the intrinsic dynamical features. The TDDVR calculated PE and assigned ZEKE spectra of all CPAHs are found to be good agreement with the previous experimental data and other available theoretical results.

Photolysis-induced scrambling of PAHs as a mechanism for deuterium storage

Aims. We investigate the possible role of polycyclic aromatic hydrocarbons (PAHs) as a sink for deuterium in the interstellar medium (ISM) and study UV photolysis as a potential underlying chemical process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologs of deuterium-enriched, protonated anthracene and phenanthrene ions (both C14H10 isomers) was recorded in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Infrared multiple photon dissociation spectroscopy using the Free-Electron Laser for Infrared eXperiments was applied to provide IR spectra. Infrared spectra calculated using density functional theory were compared to the experimental data to identify the isomers present in the experiment. Transition-state energies and reaction rates were also calculated and related to the experimentally observed fragmentation product abundances. Results. The photofragmentation mass spectra for both UV and IRMPD photolysis only show the loss of atomic hydrogen from [D − C14H10]+, whereas [H − C14D10]+ shows a strong preference for the elimination of deuterium. Transition state calculations reveal facile 1,2-H and -D shift reactions, with associated energy barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes of the two different PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The ∼0.1 eV difference in zero-point energy between C–H and C–D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D atom loss. Conclusions. We conclude that scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to a strongly bound aromatic site, protecting it from elimination. We speculate that this could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C–HD group on solo sites might be responsible for the majority of aliphatic C–D stretching bands seen in astronomical spectra. An accurate photochemical model of PAHs that considers deuterium scrambling is needed to study this further.

Formation of polyynes and ring-polyyne molecules following fragmentation of polycyclic aromatic hydrocarbons

In this work, we perform molecular dynamic (MD) simulations to investigate the stability and fragmentation processes of vibrationally excited linear polycyclic aromatic hydrocarbons (PAHs). The program of CP2K in combination with the semi-empirical method PM3 is utilized for the MD simulations. The simulations show that the formation of molecular hydrogens (H2) is different than previous studies, in particular, different than compact PAHs. At high temperatures, linear PAHs tend to open aromatic rings and convert the sp3 C–C or sp2 C=C bonds to sp C≡C bonds by removing H2; i.e. polyynes are formed in such process. Besides polyynes, PAHs attached with sp-bonded polyyne chains are commonly observed at high temperatures. We notice that due to the addition of flexible tails (polyynes), the ring-polyyne molecules do not dissociate for a long period of time at high temperatures. Such structures facilitate the molecules to survive in the harsh environment of the interstellar medium. In addition, the ring-polyyne structures induce dipole moments that could, in principle, be detected by radio astronomy.

Temperature effects on anharmonic infrared spectra of large compact polycyclic aromatic hydrocarbons

Aims. Large compact polycyclic aromatic hydrocarbon molecules (PAHs) present special interest in the astrochemical community. A key issue in analyses of large PAHs is understanding the effect that temperature and anharmonicity have on different vibrational bands, and thus interpreting the infrared (IR) spectra for molecules under various conditions. Methods. Because of the huge amount of interactions/resonances in large PAHs, no anharmonic IR spectrum can be produced with static/time-independent ab initio method, especially for the molecules with D6h symmetry, e.g., coronene and circumcoronene. In this work, we performed molecular dynamics simulations to generate anharmonic IR spectra of coronene and circumcoronene. Results. The method is validated for small PAHs, i.e., naphthalene and pyrene. We find that the semiempirical method PM3 produces accurate band positions with an error &lt;5 cm−1. Furthermore, we calculate the spectra at multiple temperatures and find a clear trend toward band shifting and broadening.

The Carrier of 3.3 μm Aromatic Infrared Bands: Anharmonicity and Temperature Effects on Neutral PAHs

Abstract Anharmonic infrared (IR) spectra are crucial for the study of interstellar polycyclic aromatic hydrocarbon (PAH) molecules. This work aims to provide a comprehensive study of the features that may influence the accuracy of anharmonic IR spectra of PAHs so that a reliable spectrum that incorporates all necessary features for interpreting the observational IR spectra can be obtained. Six PAHs are investigated: naphthalene, anthracene, pyrene, chrysene, 9,10-dimethylanthracene, and 9,10-dihydroanthracene. The NIST spectra and high-resolution IR absorption spectra are utilized as the reference for the comparisons. The influences of different resonances and resonant thresholds are studied. Four methods for electronic structure calculations are tested. The quantitative comparisons indicate that for the NIST data, B3LYP/N07D provides the best agreement with measured spectra concerning band positions and B3LYP/cc-pVTZ is superior in the description of the relative intensities. The importance of 1–3 Darling–Dennison resonances, which are required for generating triple combination bands, is investigated through a comparison to a high-resolution experimental spectrum. For interpreting the bandwidths and profiles of the observational spectra, the temperature effects are included through the Wand-Landau random walk technique. The comparisons between calculated high-temperature anharmonic and observational spectra indicate that small and compact PAHs might be responsible for the 3.3 μm aromatic infrared bands.

Raman spectroscopy of dispersed vitrinite — Methodical aspects and correlation with reflectance

Raman spectroscopy of dispersed vitrinites needs polished surfaces to safely identify organic particles in whole rock samples. Carbonaceous matter (CM) is very sensitive to the polishing process which leads to erroneous Raman spectra of these materials. It is unknown to which extent Raman spectra of low ordered CM are influenced by the polishing process. Therefore, vitrinites of high volatile bituminous coal, through anthracite to semi-graphite rank to graphitic CM were analyzed by multi-wavelength Raman spectroscopy and measured for minimum and maximum reflectance. A step-wise preparation and measuring protocol allows us to access at which point the Raman spectra are altered by sample preparation. The effect of polishing on the Raman spectra of vitrinites is not significant up to maximum reflectance values of ~7%. The multi-wavelength approach shows that short-wavelength lasers (488nm and less) invoke far less fluorescence background than long-wavelength lasers, which permits us to measure very low mature vitrinites. Wavelength-dependent frequency shifts in the vitrinite Raman spectra reconstruct a two stage evolution of aromatic compounds during organic metamorphism. The first stage shows a wavelength independent downshift of the defect-band (D-band) from ~1370 to 1330cm−1, which is assumed to be related to the progressive growth of linear aromatic structures. The second stage is characterized by diverging D-band positions, which is caused by the growth of compact polycyclic aromatic hydrocarbons. Consequently, a strong linear correlation between the reflectance values and the derived Raman spectroscopic parameters was found. Because the comparison was conducted on the single grain level, it is shown that the scaled total area (STA) Raman parameter relates to the true maximum vitrinite reflectance. Thus, a linear and robust maturity index, which covers a maximum vitrinite reflectance range of ca. 1 to 7%, is established.

The infrared spectra of nonplanar polycyclic aromatic hydrocarbons with five- or seven-membered rings

The infrared (IR) spectra are computed for compact polycyclic aromatic hydrocarbons (PAHs) with one five- or one seven-membered central ring, which have a bowl and saddle shape, respectively. In spite of the large geometric distortion compared with the planar PAHs with only six-membered rings, the IR spectra are surprisingly similar. Species with more than one five-membered ring show larger difference compared with typical PAHs. The C–C modes in the “ball” shaped C60 and C70 are shifted somewhat from those in typical PAHs. The ions of C60 and C70 show the typical enhancement of these modes compared with neutrals. Cases where the B3LYP method fail are discussed as is the choice of functional.

First results of the ORGANIC experiment on EXPOSE-R on the ISS

AbstractThe ORGANIC experiment on EXPOSE-R spent 682 days outside the International Space Station, providing continuous exposure to the cosmic-, solar- and trapped-particle radiation background for fourteen samples: 11 polycyclic aromatic hydrocarbons (PAHs) and three fullerenes. The thin films of the ORGANIC experiment received, during space exposure, an irradiation dose of the order of 14 000 MJ m−2 over 2900 h of unshadowed solar illumination. Extensive analyses were performed on the returned samples and the results compared to ground control measurements. Analytical studies of the returned samples included spectral measurements from the vacuum ultraviolet to the infrared range and time-of-flight secondary ion mass spectrometry. Limited spectral changes were observed in most cases pointing to the stability of PAHs and fullerenes under space exposure conditions. Furthermore, the results of these experiments confirm the known trend in the stability of PAH species according to molecular structure: compact PAHs are more stable than non-compact PAHs, which are themselves more stable than PAHs containing heteroatoms, the last category being the most prone to degradation in the space environment. We estimate a depletion rate of the order of 85 ± 5% over the 17 equivalent weeks of continuous unshadowed solar exposure in the most extreme case tetracene (smallest, non-compact PAH sample). The insignificant spectral changes (below 10%) measured for solid films of large or compact PAHs and fullerenes indicate a high stability under the range of space exposure conditions investigated on EXPOSE-R.

Conformational dynamics and finite-temperature infrared spectra of the water octamer adsorbed on coronene

We present in this work a detailed study of all-atoms conformational dynamics and finite temperature infrared (IR) spectra of the water octamer (H2O)8 adsorbed on coronene (C24H12), a compact Polycyclic Aromatic Hydrocarbon (PAH). The potential energy surface is calculated on-the-fly within the self-consistent-charge density-functional based tight-binding (SCC–DFTB) approach, with modifications insuring the correct description of water–water and water–PAH interactions. On-the-fly Born–Oppenheimer molecular dynamics simulations are performed in the temperature T range 10–300K starting from the most stable cubic conformer of (H2O)8 adsorbed on C24H12. As T increases, diffusion of (H2O)8 starts, followed by isomerisation processes and “melting” of (H2O)8 for T in the range 150–200K. These dynamical processes are quantified through the temperature evolution of chosen indicators. We show that the adsorption of (H2O)8 on C24H12 leads to lower isomerisation temperatures than for the bare cluster, in line with an increase of the density of isomers. A comparative analysis of the low-T (harmonic) spectra of bare and adsorbed (H2O)8 is provided. Finally, the evolution of the spectra as a function of T, illustrating the conformational dynamics, is discussed.

Water clusters adsorbed on polycyclic aromatic hydrocarbons: Energetics and conformational dynamics

In this work, we present some classical molecular dynamics (MD) simulations and finite temperature infrared (IR) spectra of water clusters adsorbed on coronene (C24H12), a compact polycyclic aromatic hydrocarbon (PAH). The potential energy surface is obtained within the self-consistent-charge density-functional based tight-binding approach with modifications insuring the correct description of water-water and water-PAH interactions. This scheme is benchmarked for the minimal energy structures of (C24H12)(H2O)n (n = 3-10) against density-functional theory (DFT) calculations and for the low-energy isomers of (H2O)6 and (C6H6)(H2O)3 against correlated wavefunction and DFT calculations. A detailed study of the low energy isomers of (C24H12)(H2O)3, 6 complexes is then provided. On-the-fly Born-Oppenheimer MD simulations are performed in the temperature T range 10-350 K for (C24H12)(H2O)n (n = 3-7) complexes. The description of the evolution of the systems with T is provided with emphasis on (C24H12)(H2O)n (n = 3,6). For T in the range 50-150 K, isomerisation processes are observed and when T increases, a solid-to-liquid phase-change like behavior is shown. The desorption of one water molecule is frequently observed at 300 K. The isomerisation processes are evidenced on the finite temperature IR spectra and the results are presented for (C24H12)(H2O)n (n = 3,6). A signature for the edge-coordination of the water cluster on the PAH is also proposed.

PROPERTIES OF POLYCYCLIC AROMATIC HYDROCARBONS IN THE NORTHWEST PHOTON DOMINATED REGION OF NGC 7023. I. PAH SIZE, CHARGE, COMPOSITION, AND STRUCTURE DISTRIBUTION

Polycyclic aromatic hydrocarbon (PAH) emission in the Spitzer Infrared Spectrograph spectral map of the northwest photon dominated region (PDR) in NGC 7023 was analyzed exclusively using PAH spectra from the NASA Ames PAH IR Spectroscopic Database (www.astrochem.org/pahdb). The 5-15 μm spectrum at each pixel is fitted using a non-negative-least-squares fitting approach. The fits are of good quality, allowing decomposition of the PAH emission into four subclasses: size, charge, composition, and hydrogen adjacency (structure). Maps tracing PAH subclass distributions across the region paint a coherent astrophysical picture. Once past some 20 seconds of arc from HD 200775, the emission is dominated by the more stable, large, symmetric, compact PAH cations with smaller, neutral PAHs taking over along the lines-of-sight toward the more distant molecular cloud. The boundary between the PDR and the denser cloud material shows up as a distinct discontinuity in the breakdown maps. Noteworthy is the requirement for PANH cations to fit the bulk of the 6.2 and 11.0 μm features and the indication of PAH photo-dehydrogenation and fragmentation close to HD 200775. Decomposition of the spectral maps into principal subclass template spectra provides additional insight into the behavior of each subclass. However, the general applicability of this computationally more efficient approach is presently undetermined. This is the first time the spectra of individual PAHs are exclusively used to fit the 5-15 μm region and analyze the spatial behavior of the aromatic infrared bands, providing fundamental, new information about astronomical PAH subpopulations including their dependence on, and response to, changes in local conditions.

Evolution of polycyclic aromatic hydrocarbons in photodissociation regions

Various studies have emphasized variations of the charge state and composition of the interstellar polycyclic aromatic hydrocarbon (PAH) population in photodissociation regions (PDRs). We aim to model the spatial evolution of the charge and hydrogenation states of PAHs in PDRs. We focus on the specific case of the north-west (NW) PDR of NGC 7023 and also discuss the case of the diffuse interstellar medium (ISM). The physical conditions in NGC 7023 NW are modelled using a state-of-the-art PDR code. We then use a new PAH chemical evolution model that includes recent experimental data on PAHs and describes multiphoton events. We consider a family of compact PAHs bearing up to 96 carbon atoms. The calculated ionization ratio is in good agreement with observations in NGC 7023 NW. Within the PDR, PAHs evolve into three major populations: medium-sized PAHs (50<Nc<90) are normally hydrogenated, larger PAHs (Nc>90) can be superhydrogenated, and smaller species (Nc<50) are fully dehydrogenated. In the cavity, where the fullerene C60 was recently detected, all the studied PAHs are found to be quickly fully dehydrogenated. PAH chemical evolution exhibits a complex non-linear behaviour as a function of the UV radiation field because of multiphoton events. Steady state for hydrogenation is reached on timescales ranging from less than a year for small PAHs, up to 10000 years for large PAHs at Av=1. We identified critical reactions that need more studies. Our new model allows us to rationalize the observational constraints without any fitting parameter. PAHs smaller than 50 carbon atoms are not expected to survive in the NGC 7023 NW PDR. A similar conclusion is obtained for the diffuse ISM. Carbon clusters turn out to be end products of PAH photodissociation, and the evolution of these clusters needs to be investigated further to evaluate their impact on the chemical and physical evolution of PDRs.

THE INFRARED SPECTROSCOPY OF COMPACT POLYCYCLIC AROMATIC HYDROCARBONS CONTAINING UP TO 384 CARBONS

The mid- and the far-infrared spectra of polycyclic aromatic hydrocarbons (PAHs) have been computed using density functional theory. This study has focused on PAHs in the highly symmetric, compact, coronene family with sizes up to 384 carbons. We have identified trends in the peak position and intrinsic strength of the vibrational modes of these species and compared these to trends previously reported for less symmetric and smaller PAHs. The computed spectral modes have been used to calculate the IR emission spectrum of PAHs pumped by UV photons. The results have been compared to observed interstellar spectra to elucidate the characteristics of the interstellar PAH family. The calculations show that highly symmetric PAHs are very stable and, hence, might be favored under the harsh conditions of interstellar space. Our calculated vibrational properties confirm and extend previous studies for small PAHs to the large compact PAHs studied here, specifically in terms of the dependence of the spectral characteristics on ionization and on H-adjacency. The calculations show that for PAHs larger than 150 carbons, the 6.3 {mu}m feature becomes very broad and shifts to longer wavelengths, the 8.6 {mu}m band becomes stronger than the '7.7' {mu}m band, and the 11.0/12.7 band strength ratiomore » gets too large compared with observations. Thus, PAHs with 150 carbons or more are unlikely to be the dominant species in interstellar space. The simplicity of the observed spectra in the 15-20 {mu}m range points toward a preponderance of compact PAHs in the interstellar PAH family.« less

Vibrational spectroscopy and molecular dynamics of water monomers and dimers adsorbed on polycyclic aromatic hydrocarbons

This paper reports structures, energetics, dynamics and spectroscopy of H2O and (H2O)2 systems adsorbed on coronene (C24H12), a compact polycyclic aromatic hydrocarbon (PAH). On-the-fly Born-Oppenheimer molecular dynamics simulations are performed for temperatures T varying from 10 to 300 K, on a potential energy surface obtained within the self-consistent-charge density-functional based tight-binding (SCC-DFTB) approach. Anharmonic infrared (IR) spectra are extracted from these simulations. We first benchmark the SCC-DFTB semi-empirical hamiltonian vs. DFT (Density Functional Theory) calculations that include dispersion, on (C6H6)(H2O)1,2 small complexes. We find that charge corrections and inclusion of dispersion contributions in DFTB are necessary to obtain consistent structures, energetics and IR spectra. Using this Hamiltonian, the structures, energetics and IR features of the low-energy isomers of (C24H12)(H2O)1,2 are found to be similar to the DFT ones, with evidence for a stabilizing edge-coordination. The temperature dependence of the motions of H2O and (H2O)2 on the surface of C24H12 is analysed, revealing ultra-fast periodic motion. The water dimer starts diffusing at a higher temperature than the water monomer (150 K vs. 10 K respectively), which appears to be consistent with the binding energies. Qualitative and quantitative analyses of the effects of T on the IR spectra are performed. Anharmonic factors in particular are derived and it is shown that they can be used as signatures for the presence of PAH-water complexes. Finally, this paper lays the foundations for the studies of larger (PAH)m(H2O)n clusters, that can be treated with the efficient computational approach benchmarked in this paper.

The 15–20 μm PAH emission features: probes of individual PAHs?

Context. Spectral features between about 15−20 μm are commonly associated with polycyclic aromatic hydrocarbons (PAHs). With the NASA Spitzer Space Telescope these features are reported routinely, and as such, warrant a deeper molecular explanation. Aims. We aim to determine the characteristics of the group of carriers of the plateau and the distinct sub-features at 15.8, 16.4, 17.4, 17.8 and 18.9 μm and to draw astronomical implications from these spectra. Methods. We analyse and interpret the spectra of 15 different sources using the NASA Ames PAH IR spectroscopic database. Results. The bands within the 15−20 μm region show large variations. Except for the 16.4 μm band, there is also no connection, both in band strength and feature classification, with the mid-IR PAH bands. Of the PAH spectra considered, only those from species containing pendent rings show one “common” characteristic: a band near the astronomical 16.4 μm position. However, coupling with the carbon skeleton’s core influences its precise position in the spectrum. Compact PAHs in the size range 50−130 carbon atoms, consistently show a strong band near the astronomical 17.4 μm band position. Conclusions. The 15−20 μm region is the transition zone from PAH nearest neighbour modes to full-skeleton modes. We conclude that a few individual PAHs dominate the astronomical PAH family when clear features are prominent. In the few cases of a broad plateau, the PAH family would be far richer. Although PAHs containing pendent rings showed promise explaining the astronomical 16.4 μm band, coupling with the skeleton core and the inherent strong quartet mode expected around 13.5 μm, make it a less viable candidate. The number of large PAHs in the database becomes a limitation in studying the emission between 15−20 μm and longward. Computation of larger PAH spectra should therefore be stimulated, especially for understanding the forthcoming far-IR data expected from Herschel, SOFIA and ALMA.

Cavity ring-down spectroscopy and theoretical calculations of the S1(B3u1)←S(Ag1) transition of jet-cooled perylene

As part of our long-term program to test the diffuse interstellar band-polycyclic aromatic hydrocarbon hypothesis, we have investigated the S(1)<--S(0) electronic transition of neutral perylene (C(20)H(12)) in a combined experimental and theoretical study. Jet-cooled perylene was prepared with a pulsed discharge slit nozzle and detected by cavity ring-down spectroscopy. A number of vibronic features were observed in the 24 000-24 900 cm(-1) spectral range. Density functional and ab initio calculations were performed to determine the geometries, harmonic vibrational frequencies, and normal coordinates of both the S(0) and S(1) electronic states. A rotational temperature of 52+/-5 K was derived from a rotational contour analysis of the vibronic band associated with the 0-0 transition. A Franck-Condon treatment was carried out to calculate the vibronic spectrum of the S(1)<--S(0) transition. A good agreement was found between the calculated and the experimental spectra. A vibrational assignment is proposed and six normal modes are identified. The contribution of neutral compact polycyclic aromatic hydrocarbons to the diffuse interstellar bands is briefly discussed.