Nuclear Magnetic Resonance (NMR) is one of the most powerful experimental techniques to characterize the structure of molecules and confined liquids. Nevertheless, the complexity of the systems under investigation usually requires complementary computational studies to interpret the NMR results. In this work we focus on polycyclic aromatic hydrocarbons (PAHs), an important class of organic molecules which have been commonly used as simple analogues for the spectroscopic properties of more complex systems, such as porous disordered carbons. We use Density Functional Theory (DFT) to calculate 13C chemical shifts and Nucleus Independent Chemical Shifts (NICS) for 34 PAHs. The results show a clear molecular size dependence of the two quantities, as well as the convergence of the 13C NMR shifts towards the values observed for graphene. We then present two computationally cheap models for the prediction of NICS in simple PAHs. We show that while a simple dipolar model fails to produce accurate values, a perturbative tight-binding approach can be successfully applied for the prediction of NICS in this series of molecules, including some non-planar ones containing 5- and 7-membered rings. This model, one to two orders of magnitudes faster than DFT calculations, is very promising and can be further refined in order to study more complex systems.
Dimerization of polycyclic aromatic hydrocarbons (PAHs) is an important, yet poorly understood, step in the on-surface synthesis of graphene (nanoribbon), soot formation, and growth of carbonaceous dust grains in the interstellar medium (ISM). The on-surface synthesis of graphene and the growth of carbonaceous dust grains in the ISM require the chemical dimerization in which chemical bonds are formed between PAH monomers. An accurate and cheap method of exploring structure rearrangements is needed to reveal the mechanism of chemical dimerization on surfaces. This work has investigated the chem…
Recently reported anomalies in the double-photonionization spectra of aromatic molecules such as benzene, naphthalene, anthracene and coronene are attributed to Coulomb-pair resonances of pi electrons.
The electronic and optical properties of various polycyclic aromatic hydrocarbons (PAHs) with lower symmetry, namely, benzo[ghi]perylene (C$_{22}$H$_{12}$), benzo[a]coronene (C$_{28}$H$_{14}$), naphtho[2,3a]coronene (C$_{32}$H$_{16}$), anthra[2,3a]coronene (C$_{36}$H$_{18}$), and naphtho[8,1,2-abc]coronene (C$_{30}$H$_{14}$) were investigated. For the purpose, we performed electron-correlated calculations using screened, and standard parameters in the $π$-electron Pariser-Parr-Pople (PPP) Hamiltonian, and the correlation effects were included, both for ground and excited states, using the mult…
In this Letter we report the results of density functional theory calculations on medium-sized neutral Polycyclic Aromatic Hydrocarbon (PAH) molecules with armchair edges. These PAH molecules possess strong C-H stretching and bending modes around 3 μm and in the fingerprint region (10-15 μm), and also strong ring deformation modes around 12.7 μm. Perusal of the entries in the NASA Ames PAHs Database shows that ring deformation modes of PAHs are common - although generally weak. We then propose that armchair PAHs with NC >65 are responsible for the 12.7 μm Aromatic Infrared Band in HII regions …
We investigate the role of Kekule and non-Kekule structures in the radical character of alternant polycyclic aromatic hydrocarbons (PAHs) using thermally-assisted-occupation density functional theory (TAO-DFT), an efficient electronic structure method for the study of large ground-state systems with strong static correlation effects. Our results reveal that the studies of Kekule and non-Kekule structures qualitatively describe the radical character of alternant PAHs, which could be useful when electronic structure calculations are infeasible due to the expensive computational cost. In addition…
Present routes to produce magnetic organic-based materials adopt a common strategy: the use of magnetic species (atoms, polyradicals, etc.) as building blocks. We explore an alternative approach which consists of selective hydrogenation of Polycyclic Aromatic Hydrocarbons. Self-Consistent-Field (SCF) (Hartree-Fock and DFT) and multi-configurational (CISD and MCSCF) calculations on coronene and corannulene, both hexa-hydrogenated, show that the formation of stable high spin species is possible. The spin of the ground states is discussed in terms of the Hund rule and Lieb's theorem for bipartite…
A method for study of charge-transfer interactions between solute molecules and solvent based on the comparison of the ratios of spectral shifts of different electronic transitions in solute molecules in chemically inert solvent is proposed. The method is applicable to molecules that do not change their dipole moment on excitation. As an example, a presence of charge transfer interactions in higher electronic states of aromatic hydrocarbons (benzene, phenanthrene, and naphthalene) dissolved in water and alcohols was demonstrated.
Combinatorial introduction of heteroatoms in the two-dimensional framework of aromatic hydrocarbons opens up possibilities to design compound libraries exhibiting desirable photovoltaic and photochemical properties. Exhaustive enumeration and first-principles characterization of this chemical space provide indispensable insights for rational compound design strategies. Here, for the smallest seventy-seven Kekulean-benzenoid polycyclic systems, we reveal combinatorial substitution of C atom pairs with the isosteric and isoelectronic B, N pairs to result in 7,453,041,547,842 (7.4 tera) unique mo…
New research is presented, and previous research is reviewed, on the emission and absorption of interstellar aromatic hydrocarbons. Emission from aromatic hydrocarbons dominate the mid-infrared emission of many galaxies, including our own Milky Way galaxy. Only recently have aromatic hydrocarbons been observed in absorption in the interstellar medium, along lines of sight with high column densities of interstellar gas and dust. Much work on interstellar aromatics has been done, with astronomical observations and laboratory and theoretical astrochemistry. In many cases the predictions of labora…
This joint theoretical and experimental study establishes that the adsorption of polycyclic aromatic hydrocarbons (PAHs) onto the amorphous ice surface provokes a broadening and redshift of the "dangling" OH (dOH) ice spectral feature, the redshift increasing with PAH size up to $\sim$ 85~cm$^{-1}$. It also reveals that, in certain interaction configurations, adsorption induces substantial reorganisation of the hydrogen-bonding network at the ice surface. Comparison with experiments validates the novel theoretical methodology relying on the density functional based tight binding approach, whic…
The electronic and optical properties of polycyclic aromatic hydrocarbons (PAHs) present a strong dependence on their size and geometry. We tackle this issue by analyzing the spectral features of two prototypical classes of PAHs, belonging to D6h and D2h symmetry point groups and related to coronene as multifunctional seed. While the size variation induces an overall red shift of the spectra and a redistribution of the oscillator strength between the main peaks, a lower molecular symmetry is responsible for the appearance of new optical features. Along with broken molecular orbital degeneracie…
A recent study of soft X-ray absorption in native and hydrogenated coronene cations, C$_{24}$H$_{12+m}^+$ $m=0-7$, led to the conclusion that additional hydrogen atoms protect (interstellar) Polycyclic Aromatic Hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014)]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C$_{16}$H$_{10+m}^+$, $m=0$, 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not d…
Mixtures of polycylic aromatic hydrocarbons (PAHs) have been produced by means of laser pyrolysis. The main fraction of the extracted PAHs were primarily medium-sized, up to a maximum size of 38 carbon atoms per molecule. The use of different extraction solvents and subsequent chromatographic fractionation provided mixtures of different size distributions. UV-VIS absorption spectra have been measured at low temperature by matrix isolation spectroscopy and at room temperature with PAHs as film-like deposits on transparent substrates. In accordance with semi-empirical calculations, our findings …
We analyze resonances in the double photoionization of a variety of aromatic hydrocarbons. The resonances reflect the breakup of quasi-bound electron pairs. The basic premise of this paper is that there is a direct connection between the quasi-bound pairs and resonant peaks in the optical absorption that are associated with doubly occupied sites on the perimeter and inside the perimeter of the molecule. The optical absorption leading to the high-energy resonance (approximately 40 eV), calculated from a many-site one-dimensional Hubbard model, has a peak at U, the electrostatic interaction ener…
In recent years Polycyclic Aromatic Hydrocarbons (PAHs) have been studied for their electronic properties as they are viewed as nanodots of graphene. They have also been of interest as functional molecules for applications such as light emitting diodes and solar cells. Since last few years varying structural and chemical properties corresponding to the size and geometry of these molecules have been studied both theoretically and experimentally. In this paper, we carry out a systematic study of the electronic states of several PAHs using the Pariser-Parr-Pople model which incorporates long-rang…
The work is devoted to the adaptation of the results of laboratory studies of the laser-induced dissociation of molecules of benzene adsorbed on a quartz substrate to the conditions of the interstellar medium. Adsorption was performed under conditions of low temperature and deep vacuum. The difference between the photolysis of adsorbed molecules and molecules in the gas phase is identified. Significance of process of photolytic desorption in the interstellar conditions is analyzed, in particular, in the conditions of photodissociation regions. It is shown that the efficiency and dissociation c…
We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micron CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold (~4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of th…
Void induced coronene C23H12++ was suggested to be a possible carrier of the astronomically observed polycyclic aromatic hydrocarbon (PAH), which shows unique molecular structure with carbon two pentagons connected with five hexagons. Well observed astronomical infrared spectrum from 3-15 micron could be almost reproduced based on density functional theory. However, there remain several discrepancies with observed spectra, especially on 11-15 micron band weaker intensity. Observed 11.2 micron intensity is comparable to 7.6-7.8 micron one. Methyl-modified molecule C24H14++ revealed that calcula…
Aims. In this work we determine the effects of anharmonicity on the mid-infrared spectra of the linear polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, tetracene and pentacene recorded using the free electron laser FELIX. Methods. Comparison of experimental spectra obtained under supersonic jet conditions with theoretically predicted spectra was used to show if anharmonicity explicitly needs to be taken into account. Results. Anharmonic spectra obtained using second-order vibrational perturbation theory agree on average within 0.5% of the experimental frequencies. Importantly, …
Institut Lumière Matière（光与物质研究所）；Université Lyon 1-CNRS（里昂第一大学-法国国家科学研究中心）；Université de Lyon（里昂大学）；Center for Nonlinear Phenomena and Complex Systems（非线性现象与复杂系统中心）；Université Libre de Bruxelles（布鲁塞尔自由大学）；Institut des Sciences Moléculaires d’Orsay (ISMO)（奥赛分子科学研究所（ISMO））；Université Paris-Saclay（巴黎萨克雷大学）
The Interest in polycyclic aromatic hydrocarbons (PAHs) spans numerous fields and infrared spectroscopy is usually the method of choice to disentangle their molecular structure. In order to compute vibrational frequencies, numerous theoretical studies employ either quantum calculation methods, or empirical potentials, but it remains difficult to combine the accuracy of the first approach with the computational cost of the second. In this work, we employed Machine Learning techniques to develop a potential energy surface and a dipole mapping based on an artificial neural network (ANN) architect…
Clusters of polycyclic aromatic hydrocarbon (PAH) molecules are modelled using explicit all-atom potentials using a rigid body approximation. The PAH's considered range from pyrene (C10H8) to circumcoronene (C54H18), and clusters containing between 2 and 32 molecules are investigated. In addition to the usual repulsion-dispersion interactions, electrostatic point-charge interactions are incorporated, as obtained from density functional theory calculations. The general electrostatic distribution in neutral or singly charged PAH's is reproduced well using a fluctuating charges analysis, which pr…
We have measured absolute cross sections for ultrafast (fs) single-carbon knockout from Polycyclic Aromatic Hydrocarbon (PAH) cations as functions of He-PAH center-of-mass collision energy in the range 10-200 eV. Classical Molecular Dynamics (MD) simulations cover this range and extend up to 10$^5$ eV. The shapes of the knockout cross sections are well described by a simple analytical expression yielding experimental and MD threshold energies of $E_{th}^{Exp}=32.5\pm 0.4$ eV and $E_{th}^{MD}=41.0\pm 0.3$ eV, respectively. These are the first measurements of knockout threshold energies for mole…
Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH3), methylene (>CH2), or diamond-like *CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-f…
Benzene (C6H6) and polycyclic hydrocarbons such as naphthalene (C10H8), anthracene (C14H10) and coronene (C24H12) are well known aromatic organic compounds. We study the substitution of Li replacing all H atoms in these hydrocarbons using density functional method. The vertical ionization energy (VIE) of such lithiated species, i.e., C6Li6, C10Li8, C14Li10 and C24Li12 ranges 4.24-4.50 eV, which is lower than the IE of Li atom. Thus, these species may behave as superalkalis, due to their lower IE than alkali metal. However, these lithiated species possess planar and closed-shell structure, unli…
In this work we report on high-resolution IR absorption studies that provide a detailed view on how the peripheral structure of irregular polycyclic aromatic hydrocarbons (PAHs) affects the shape and position of their 3 μm absorption band. To this purpose we present mass-selected, high-resolution absorption spectra of cold and isolated phenanthrene, pyrene, benz[a]antracene, chrysene, triphenylene, and perylene molecules in the 2950-3150 cm-1 range. The experimental spectra are compared with standard harmonic calculations, and anharmonic calculations using a modified version of the SPECTRO pro…
Aims. Due to the limitations of current computational technology, the fragmentation and isomerization products of vibrationally-excited polycyclic aromatic hydrocarbon (PAH) molecules and their derivatives are poorly studied. In this work, we investigate the intermediate products of PAHs and their derivatives as well as the gas-phase reactions relevant to the interstellar medium, with coronene as a case study. Methods. Based on the semi-empirical method of PM3 as implemented in the CP2K program, molecular dynamics simulations are performed to model the major processes (e.g., vibrations, fragme…
In order to find out capable chemical evolution step from astronomically created organic in interstellar space to biological organic on the earth, infrared spectrum of nitrogen substituted carbon pentagon-hexagon coupled polycyclic aromatic hydrocarbon was analyzed by the density functional theory. Ionization was modeled from neutral to tri-cation. Among one nitrogen and two nitrogen substituted NPAH, we could find good examples showing similar IR behavior with astronomically well observed one as like C8H6N1, C7H5N2, and C7H5N2. We can imagine that such ionized NPAH may be created in interstel…
We report on a common fragment ion formed during the electron-ionization-induced fragmentation of three different three-ring polycyclic aromatic hydrocarbons (PAHs), fluorene (C$_{13}$H$_{10}$), 9,10-dihydrophenanthrene (C$_{14}$H$_{12}$), and 9,10-dihydroanthracene (C$_{14}$H$_{12}$). The infrared spectra of the mass-isolated product ions with $m/z=165$ were obtained in a Fourier transform ion cyclotron resonance mass spectrometer whose cell was placed inside the optical cavity of an infrared free-electron laser, thus providing the high photon fluence required for efficient infrared multiple-…
By applying quantum chemical calculation, interstellar infrared spectrum was categorized to three classes. Type-A show unusual feature of strong peaks at 11.3,12.9, and 14.0 micrometer. Usually observed 6.2, 7.7, and 8.6 micrometer bands are weak or not recognized. Typical examples are NGC1316 and NGC4589. Such spectrum could be identified for the first time by pure carbon molecule (C23)2+ (dication) having two carbon pentagons combined with five hexagons. Calculated spectrum coincided well at 11.3, 13.0, and 14.0 micrometer. Also we could find more coincidence at 5.2, 5.6, 7.6, 8.8,10.6,15.7 …
In order to find out capable molecular source of astronomically well observed infrared (IR) spectrum, asymmetric molecular configuration polycyclic aromatic hydrocarbon (PAH) was analyzed by the density functional theory (DFT) analysis. Starting molecules were benzene C6H6, naphthalene C10H8 and 1H-phenalene C13H9. In interstellar space, those molecules will be attacked by high energy photon and proton, which may bring cationic molecules as like C6H6n+ (n=0~3 in calculation), C10H8n+, and C13H9n+, also CH lacked molecules C5H5n+, C9H7n+, and C12H8n+. IR spectra of those molecules were analyzed…
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 requires careful consideration when pr…
The life cycle of the population of interstellar polycyclic aromatic hydrocarbon (PAH) molecules depends partly on the photostability of the individual species. We have studied the dissociative photoionization of two ethynyl-substituted PAH species, namely, 9-ethynylphenanthrene and 1-ethynylpyrene. Their adiabatic ionization energy and the appearance energy of fragment ions have been measured with the photoelectron photoion coincidence (PEPICO) spectroscopy technique. The adiabatic ionization energy has been found at 7.84 +/- 0.02 eV for 9-ethynylphenanthrene and at 7.41 +/- 0.02 eV for 1-eth…
The equilibrium carbon-carbon bond lengths in $π$-electron hydrocarbons are very sensitive to the electronic ground-state characteristic. In the recent two papers by Stolarczyk and Krygowski (to appear soon) a simple quantum approach, the Augmented Hückel Molecular Orbital (AugHMO) model, is proposed for the qualitative, as well as quantitative, study of this phenomenon. The simplest realization of the AugHMO model is the Hückel-Su-Schrieffer-Heeger (HSSH) method, in which the resonance integral $β$ of the HMO model is a linear function the bond length. In the present paper the HSSH method is …
While powerful techniques exist to accurately account for anharmonicity in vibrational molecular spectroscopy, they are computationally very expensive and cannot be routinely employed for large species and/or at non- zero vibrational temperatures. Motivated by the study of Polycyclic Aromatic Hydrocarbon (PAH) emission in space, we developed a new code, which takes into account all modes and can describe all IR transitions including bands becoming active due to resonances as well as overtones, combination and difference bands. In this article, we describe the methodology that was implemented a…
Polycyclic aromatic hydrocarbon (PAH) molecules, as revealed by the distinctive set of emission bands at 3.3, 6.2, 7.7, 8.6, 11.3 and 12.7 $μ$m characteristic of their vibrational modes, are abundant and widespread throughout the Universe. They are ubiquitously seen in a wide variety of astrophysical regions, ranging from planet-forming disks around young stars to the interstellar medium (ISM) of the Milky Way and external galaxies out to high redshifts at z>4. PAHs profoundly influence the thermal budget and chemistry of the ISM by dominating the photoelectric heating of the gas and controlli…
The distinctive set of infrared (IR) emission bands at 3.3, 6.2, 7.7, 8.6, and 11.3μm are ubiquitously seen in a wide variety of astrophysical environments. They are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, not a single PAH species has yet been identified in space, as the mid-IR vibrational bands are mostly representative of functional groups and thus do not allow one to fingerprint individual PAH molecules. In contrast, the far-IR (FIR) bands are sensitive to the skeletal characteristics of a molecule, hence they are important for chemical identificati…
Functionalized polcyclic aromatic hydrocarbons (PAHs) are an interesting class of molecules in which the electronic state of the graphene-like hydrocarbon part is tuned by the functional group. Searching for new types of donor and acceptor molecules, a set of new PAHs has recently been investigated experimentally using ultraviolet photoelectron spectroscopy (UPS). In this work, the electronic structure of the PAHs is studied numerically with the help of B3LYP hybrid density functionals. Using the DELTA-SCF method, electron binding energies have been determined which affirm, specify and complem…
Interstellar infrared observation shows featured spectrum due to polycyclic aromatic hydrocarbon (PAH)at wavelength 3.3,6.2,7.6,7.8,8.6,and 11.3 micrometer,which are ubiquitously observed in many astronomical dust clouds and galaxies. Our previous first principles calculation revieled that viod induced coronene (C23H12)2+ and circumcoronene (C53H18)1+ could reproduce such spectrum very well. In this study, quantum-mechanic origin was studied through atomic configuration change and atomic vibration mode analysis. By a high speed particle attack, carbon void would be introduced in PAH. Molecular…
Fragmentation is an important decay mechanism for polycyclic aromatic hydrocarbons (PAHs) under harsh interstellar conditions and represents a possible formation pathway for small molecules such as H2, C2H2, C2H4. Our aim is to investigate the dissociation mechanism of superhydrogenated PAHs that undergo energetic processing and the formation pathway of small hydrocarbons. We obtain, experimentally, the mass distribution of protonated tetrahydropyrene (C16H15 , py+5H+) and protonated hexahydropyrene (C16H17+, py+7H+) upon collision induced dissociation (CID). The IR spectra of their main fragm…
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 analyzed. 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 13.5 $μ…
The rich molecular structures of polycyclic aromatic hydrocarbons -- essentially planar flakes of fused benzene rings -- and their fullerene cousins are revealed through their vibrational and electronic spectra.
The formation mechanisms of aromatic compounds in flame are strongly influenced by the chemical and thermal history that leads to their formation. Indeed, the complex environments that characterize combustion systems do not only affect the composition of gas-phase species, but they also determine the structure and the characteristics of the soot precursors generated. To illustrate the importance of these effects, in this work we investigate the growth mechanisms of soot precursors in an atmospheric-pressure ethylene/oxygen/argon counterflow diffusion flame, using a combination of computational…
Context. The 3.3 $μ$m aromatic C-H stretching band of polycyclic aromatic hydrocarbon (PAH) molecules seen in a wide variety of astrophysical regions is often accompanied by a series of weak satellite bands at ~3.4-3.6 $μ$m. One of these sources, IRAS 21282+5050, a planetary nebula, also exhibits a weak band at ~1.68 $μ$m. While the satellite features at ~3.4-3.6 $μ$m are often attributed to the anharmonicities of PAHs, it is not clear whether overtones or combination bands dominate the 1.68 $μ$m feature. Aims. In this work, we examine the anharmonic spectra of eight PAH molecules, including a…
Detection of the Polycyclic Aromatic Hydrocarbon Phenalene (C$_{13}$H$_{10}$) in the Very Low Luminosity Object (VeLLO) MC27/L1521F
Massachusetts Institute of Technology（麻省理工学院）；Center for Astrophysics | Harvard & Smithsonian（天体物理中心 | 哈佛与史密森尼学会）；University of British Columbia（不列颠哥伦比亚大学）；National Radio Astronomy Observatory（国家射电天文台）；NSF–Simons AI Institute for Cosmic Origins（NSF-西蒙斯宇宙起源AI研究所）；University of Michigan（密歇根大学）；Worcester State University（伍斯特州立大学）；NASA Goddard Space Flight Center（美国宇航局戈达德太空飞行中心）
