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The stability and distributions of small water clusters generated in a supersonic beam expansion are interrogated by tunable vacuum ultraviolet (VUV) radiation generated at a synchrotron. Time-of-flight mass spectrometry reveals enhanced population of various protonated water clusters (H+(H2O)n) based upon ionization energy and photoionization distance from source, suggesting there are "magic" numbers below the traditional n = 21 that predominates in the literature. These intensity distributions suggest that VUV threshold photoionization (11.0-11.5 eV) of neutral water clusters close to the nozzle exit leads to a different nonequilibrium state compared to a skimmed molecular beam. This results in the appearance of a new magic number at 14. Metadynamics conformer searches coupled with modern density functional calculations are used to identify the global minimum energy structures of protonated water clusters between n = 2 and 21, as well as the manifold of low-lying metastable minima. New lowest energy structures are reported for the cases of n = 5, 6, 11, 12, 16, and 18, and special stability is identified by several measures. These theoretical results are in agreement with the experiments performed in this work in that n = 14 is shown to exhibit additional stability, based on the computed second-order stabilization energy relative to most cluster sizes, though not to the extent of the well-known n = 21 cluster. Other cluster sizes that show some additional energetic stability are n = 7, 9, 12, 17, and 19. To gain insight into the balance between ion-water and water-water interactions as a function of the cluster size, an analysis of the effective two-body interactions (which sum exactly to the total interaction energy) was performed. This analysis reveals a crossover as a function of cluster size between a water-hydronium-dominated regime for small clusters and a water-water-dominated regime for larger clusters around n = 17.
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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.
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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.
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Polyol-water clusters provide a template to probe ionization and solvation processes of paramount interest in atmospheric and interstellar chemistry. We generate glycerol water clusters in a continuous supersonic jet expansion and interrogate the neutral species with synchrotron-based tunable vacuum ultraviolet photoionization mass spectrometry. A series of glycerol fragments (m/z 44, 61, 62, and 74) clustered with water are observed. A judicious combination of backing pressure, nozzle temperature, and water vapor pressure allows for tuning the mol % of glycerol. The recorded appearance energies of the water cluster series m/z 62 and 74 are similar to that observed in pure glycerol, while the m/z 61 series shows a dependence on cluster composition. Furthermore, this series also tracks the water concentration of the beam. Theoretical calculations on neutral and ionized clusters visualize the hydrogen bond network in these water clusters and provide an assessment of the number of glycerol-glycerol, glycerol-water, and water-water hydrogen bonds in the cluster, as well as their interaction energies. This method of bond counting and interaction energy assessment explains the changes in the mass spectrum as a function of mol % and offers a glimpse of the disruption of the hydrogen bond network in glycerol-water clusters. The calculations also reveal interesting barrierless chemical processes in photoionized glycerol water clusters that are either activated or do not occur without the presence of water. Examples include spontaneous intramolecular proton transfer within glycerol to form a distonic ion, nonactivated breaking of a C-C bond, and spontaneous proton transfer from glycerol to water. These results appear relevant to radiation-induced chemical processing of alcohol-water ices in the interstellar medium.
Assuntos
Glicerol , Prótons , Gases , Ligação de Hidrogênio , VácuoRESUMO
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.
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Cooperative or nonadditive effects contribute to the pairwise noncovalent interaction of two molecules in a cluster or the condensed phase in ways that depend on the specific arrangements and interactions of the other surrounding molecules that constitute their environment. General expressions for an effective two-body interaction are presented, which are correct to increasing orders in the many-body expansion. The simplest result, correct through third order, requires only seven individual calculations, in contrast to a linear number of three-body contributions. Two applications are presented. First, an error analysis is performed on a model (H2O)8 cluster which completes the first solvation shell of a central water-water hydrogen bond. Energy decomposition analysis is performed to show that the largest effects of cooperativity on the central hydrogen bond arise from electrical polarization. Second, the nature of cooperative effects on proton transfer in an HCl + (H2O)4 cluster is characterized.
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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.
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The vibrationally resolved spectra of the pyrene cation and doubly-dehydrogenated pyrene cation (C16H10Ë+; Py+ and C16H8Ë+; 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.
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The feasibility of the compression of localized virtual orbitals is explored in the context of intramolecular long-range dispersion interactions. Singular value decomposition (SVD) of coupled cluster doubles amplitudes associated with the dispersion interactions is analyzed for a number of long-chain systems, including saturated and unsaturated hydrocarbons and a silane chain. Further decomposition of the most important amplitudes obtained from these SVDs allows for the analysis of the dispersion-specific virtual orbitals that are naturally localized. Consistent with previous work on intermolecular dispersion interactions in dimers, it is found that three important geminals arise and account for the majority of dispersion interactions at the long range, even in the many body intramolecular case. Furthermore, it is shown that as few as three localized virtual orbitals per occupied orbital can be enough to capture all pairwise long-range dispersion interactions within a molecule.
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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.
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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.
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The study of interstellar polycyclic aromatic hydrocarbons (PAHs) relies heavily on theoretically predicted infrared spectra. Most earlier studies use scaled harmonic frequencies for band positions and the double harmonic approximation for intensities. However, recent high-resolution gas-phase experimental spectroscopic studies have shown that the harmonic approximation is not sufficient to reproduce experimental results. In our previous work, we presented the anharmonic theoretical spectra of three linear PAHs, showing the importance of including anharmonicities into the theoretical calculations. In this paper, we continue this work by extending the study to include five non-linear PAHs (benz[a]anthracene, chrysene, phenanthrene, pyrene, and triphenylene), thereby allowing us to make a full assessment of how edge structure, symmetry, and size influence the effects of anharmonicities. The theoretical anharmonic spectra are compared to spectra obtained under matrix isolation low-temperature conditions, low-resolution, high-temperature gas-phase conditions, and high-resolution, low-temperature gas-phase conditions. Overall, excellent agreement is observed between the theoretical and experimental spectra although the experimental spectra show subtle but significant differences.
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Current efforts to characterize and study interstellar polycyclic aromatic hydrocarbons (PAHs) rely heavily on theoretically predicted infrared (IR) spectra. Generally, such studies use the scaled harmonic frequencies for band positions and double harmonic approximation for intensities of species, and then compare these calculated spectra with experimental spectra obtained under matrix isolation conditions. High-resolution gas-phase experimental spectroscopic studies have recently revealed that the double harmonic approximation is not sufficient for reliable spectra prediction. In this paper, we present the anharmonic theoretical spectra of three PAHs: naphthalene, anthracene, and tetracene, computed with a locally modified version of the SPECTRO program using Cartesian derivatives transformed from Gaussian 09 normal coordinate force constants. Proper treatments of Fermi resonances lead to an impressive improvement on the agreement between the observed and theoretical spectra, especially in the C-H stretching region. All major IR absorption features in the full-scale matrix-isolated spectra, the high-temperature gas-phase spectra, and the most recent high-resolution gas-phase spectra obtained under supersonically cooled molecular beam conditions in the CH-stretching region are assigned.
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A full derivation of the analytic transformation of the quadratic, cubic, and quartic force constants from normal coordinates to Cartesian coordinates is given. Previous attempts at this transformation have resulted in non-linear transformations; however, for the first time, a simple linear transformation is presented here. Two different approaches have been formulated and implemented, one of which does not require prior knowledge of the translation-rotation eigenvectors from diagonalization of the Hessian matrix. The validity of this method is tested using two molecules H2O and c-C3H2D(+).