Aromatic Hydrocarbon Molecules Research Articles

Photoelectron spectroscopy of deprotonated benzonitrile.

The recent discovery of cyano-substituted aromatic and two-ring polycyclic aromatic hydrocarbon molecules in Taurus Molecular Cloud-1 has prompted questions on how the electronic structure and excited-state dynamics of these molecules are linked with their existence and abundance. Here, we report a photodetachment and frequency- and angle-resolved photoelectron spectroscopy study of jet-cooled para-deprotonated benzonitrile (p-[Bzn-H]-). The adiabatic detachment energy was determined as 1.70 ± 0.01eV, in good agreement with CCSD(T)/aug-cc-pVTZ calculations. The spectra across the first few electron-volts above threshold are dominated by prompt autodetachment processes associated with excitation of at least five short-lived (tens of femtoseconds) temporary anion shaped resonances since excitation cross sections are several orders of magnitude larger than direct photodetachment cross sections. The photoexcitation vibronic profile is dominated by a ≈640 cm-1 ring deformation mode. [Bzn-H]- lacks a valence-localized excited state situated below the detachment threshold and does not exhibit thermionic emission following excitation of the temporary anion resonances. Thus, [Bzn-H]- is unlikely to be stable in many interstellar environments.

Gas-phase hydrogenation of large, astronomically relevant PAH cations

ABSTRACT To investigate the gas-phase hydrogenation processes of large, astronomically relevant cationic polycyclic aromatic hydrocarbon (PAH) molecules under the interstellar environments, the ion–molecule collision reaction between six PAH cations and H-atoms is studied. The experimental results show that the hydrogenated PAH cations are efficiently formed, and no even–odd hydrogenated mass patterns are observed in the hydrogenation processes. The structure of newly formed hydrogenated PAH cations and the bonding energy for the hydrogenation reaction pathways are investigated with quantum theoretical calculations. The exothermic energy for each reaction pathway is relatively high, and the competition between hydrogenation and dehydrogenation is confirmed. From the theoretical calculation, the bonding ability plays an important role in the gas-phase hydrogenation processes. The factors that affect the hydrogenation chemical reactivity are discussed, including the effect of carbon skeleton structure, the side-edged structure, the molecular size, the five- and six-membered C-ring structure, the bay region structure, and the neighbouring hydrogenation. The infrared spectra of hydrogenated PAH cations are also calculated. These results we obtain once again validate the complexity of hydrogenated PAH molecules, and provide the direction for the simulations and observations under the co-evolution interstellar chemistry network. We infer that if we do not consider other chemical evolution processes (e.g. photoevolution), then the hydrogenation states and forms of PAH compounds are intricate and complex in the interstellar medium.

Resonant electron capture by polycyclic aromatic hydrocarbon molecules: Effects of aza-substitution.

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0-15eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M-) at thermal electron energies (Ee ∼ 0eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5-2.5eV. The lifetimes (τa) of M- with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice-Ramsperger-Kassel-Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M- ions from the compounds studied is abstraction of hydrogen atoms. When studying [M-H]- ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M-H]· radicals revealed their proportionality to the EAa values of the parent molecules.

Infrared emission of specific polycyclic aromatic hydrocarbon molecules: indene

ABSTRACT Polycyclic aromatic hydrocarbon (PAH) molecules have long been suggested to be present in the interstellar medium (ISM). Nevertheless, despite their expected ubiquity and sustained searching efforts, identifying specific interstellar PAH molecules from their infrared (IR) spectroscopy has so far been unsuccessful. However, due to its unprecedented sensitivity, the advent of the JWST may change this. Meanwhile, recent years have witnessed breakthroughs in detecting specific PAH molecules (e.g. indene, cyanoindene, and cyanonaphthalene) through their rotational lines in the radio frequencies. As JWST holds great promise for identifying specific PAH molecules in the ISM based on their vibrational spectra in the IR, in this work, we model the vibrational excitation of indene, a molecule composed of a six-membered benzene ring fused with a five-membered cyclopentene ring, and calculate its IR emission spectra for a number of representative astrophysical regions. This will facilitate JWST to search for and identify indene in space through its vibrational bands and to quantitatively determine or place an upper limit on its abundance.

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

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

Study on Chemical Composition and Biological Activity of Psidium guajava Leaf Extracts.

Guava (Psidium guajava) is a plant widely distributed in tropical and subtropical regions. Its leaves contain a large amount of physiological molecules such as flavonoid, sesquiterpene, triterpenoid, coumarin, alkaloid, and tannin molecules with antioxidative and anti-inflammatory effects. In this study, the use of concentrated P. guajava leaf extract molecules as a functional natural material was evaluated by confirming the extract's antioxidative, antibacterial, tyrosinase activity inhibition, and collagenase activity inhibition effects and its trans-2-nonenal removal ability. As a result of the analysis of the antioxidant and antibacterial components of concentrated P. guajava leaf extract molecules through GC-MS, a large amount of aromatic hydrocarbon molecules were detected. When different concentrations of ethanol were used for extraction, the leaf extract concentrated with 70% ethanol showed the most effective active molecules. As a result of measuring DPPH radical scavenging activity, a concentration-dependent antioxidant activity was confirmed. The antioxidant activity tended to increase when the ethanol content used for extraction was increased. Molecules such as 2,4-di-tert-butylphenol, caryophyllene oxide, and γ-muurolene in P. guajava leaf extract concentrate appeared to have antibacterial activities against S. aureus bacteria known to cause atopy. As ethanol content increased, the inhibitory effect on tyrosinase activity was increased. In addition, when ethanol content was 50%, the concentrated leaf extract was able to remove trans-2-nonenal by 52.4%. As a result of determining the concentrated leaf extract's collagenase inhibition activity, an inhibition rate close to that of ascorbic acid, a positive control, was confirmed. The concentrated guajava leaf extract molecules were confirmed to have whitening and wrinkle-improving functionality. Thus, the P. guajava leaf extract has high potential as a food and natural cosmetic material.

Benzopyrene elimination from the environment using graphitic carbon nitride-SnS nanocomposites

Benzopyrene (BaP) stands as a potent polycyclic aromatic hydrocarbon (PAH) molecule, boasting five fused aromatic rings, making its way into the human food chain through soil contamination. The persistent environmental presence of PAHs in soil, attributed to industrial exposure, is primarily due to their low molecular weight and hydrophobic nature. To preemptively address the entry of BaP into the food chain, the application of nanocomposites was identified as an effective remediation strategy. Post-synthesis, comprehensive characterization tests employing techniques such as UV-DRS, XRD, SEM-EDX, FTIR, and DLS unveiled the distinctive features of the g–C3N4–SnS nanocomposites. These nanocomposites exhibited spherical shapes embedded on layers of nanosheets, boasting particle diameters measuring 88.9 nm. Subsequent tests were conducted to assess the efficacy of eliminating benzopyrene from a combination of PAH molecules and g–C3N4–SnS nanocomposites. Varied parameters, including PAH concentration, adsorbent dosage, and suspension pH, were systematically explored. The optimized conditions for the efficient removal of BaP utilizing the g–C3N4–SnS nanocomposite involved 2 μg/mL of benzopyrene, 10 μg/mL of the nanocomposite, and a pH of 5, considering UV light as the irradiation source. The investigation into the mechanism governing BaP elimination closely aligned with batch adsorption results involved a thorough exploration of adsorption kinetics and isotherms. Photocatalytic degradation of benzopyrene was achieved, reaching a maximum of 86 % in 4 h and 36 % in 2 h, with g–C3N4–SnS nanocomposite acting as the catalyst. Further validation through HPLC data confirmed the successful removal of BaP from the soil matrix.

Compact and accurate chemical mechanism for methane pyrolysis with PAH growth

A reliable and compact chemical mechanism of gas-phase methane pyrolysis leading to formation of large polycyclic aromatic hydrocarbon (PAH) molecules has been developed. This model is designed for studies of carbon nanostructure synthesis such as carbon black and graphene flakes, including soot growth kinetics. Methane pyrolysis with carbon nanostructure synthesis is a two-stage process where conversion of CH4 to C2H2 precedes the growth of PAH molecules from acetylene. We present a single chemical mechanism that accurately describes both stages. We have constructed a compact and accurate chemical mechanism capable of modeling both stages of methane pyrolysis based on the ABF [1] mechanism which was expanded with the most prominent reaction pathways from the mechanism by Tao [2] for small PAH molecules and HACA pathways for larger PAH molecules, up to 37 aromatic rings. The resulting mechanism was validated through comparison to multiple available sets of experimental data. Good agreement with the experimental data for both processes was obtained. Performance of the mechanism was tested for pyrolysis of methane-rich mixtures under long residence times leading to abundant formation of PAH molecules. It is shown that the inclusion of larger PAH species (up to A37) in the chemical mechanism is important for accurate prediction of the fraction of carbon converted to PAH molecules and, correspondingly, the residual fraction of acetylene in the mixture. The mechanism file is available upon request.

Infrared Emission of Specific Polycyclic Aromatic Hydrocarbon Molecules: Cyanonaphthalenes

The unidentified infrared emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μm are ubiquitously seen in a wide variety of astrophysical regions and commonly attributed to polycyclic aromatic hydrocarbon (PAH) molecules. However, the unambiguous identification of any individual, specific PAH molecules has proven elusive until very recently, when two isomers of cyanonapthalene, which consists of two fused benzene rings and substitutes a nitrile (–CN) group for a hydrogen atom, were discovered in the Taurus Molecular Cloud, based on their rotational transitions at radio frequencies. To facilitate the James Webb Space Telescope (JWST) to search for cyanonapthalenes in astrophysical regions, we model the vibrational excitation of cyanonapthalenes and calculate their infrared emission spectra in a number of representative astrophysical regions. The model emission spectra and intensities will allow JWST to quantitatively determine or place an upper limit on the abundances of cyanonapthalenes.

Hot carrier creation in a nanoparticle dimer-molecule composite.

Light-matter interactions have garnered considerable interest owing to their burgeoning applications in quantum optics and plasmonics. Utilizing first principles calculations, this work explores the hot carrier (HC) generation and distribution within a composite system made up of a plasmonic nanoparticle dimer and linear polycyclic aromatic hydrocarbon (PAH) molecules. We examine the spatial and energetic distributions of HCs by initiating photoexcitation and allowing localized surface plasmon dephasing. By positioning PAH molecules within the plasmonic nanodimer's gap region, our investigation uncovers HC tuning. Notably, depending on the size of the PAH molecules, there are significant alterations in the HC distribution. Hot electrons (HEs) are distributed across both the nanodimer and the PAH molecule, while hot holes (HHs) become entirely localized on the PAH as the PAH grows larger. These findings improve our understanding of plasmon-molecule coupled states and provide guidance on how to customize HC distributions through the creation of hybrid plasmonic materials.

The Galaxy Activity, Torus, and Outflow Survey (GATOS)

We use JWST/MIRI MRS spectroscopy of a sample of six local obscured type 1.9/2 active galactic nuclei (AGN) to compare their nuclear mid-IR absorption bands with the level of nuclear obscuration traced by X-rays. This study is the first to use subarcsecond angular resolution data of local obscured AGN to investigate the nuclear mid-IR absorption bands with a wide wavelength coverage (4.9–28.1 μm). All the nuclei show the 9.7 μm silicate band in absorption. We compare the strength of the 9.7 and 18 μm silicate features with torus model predictions. The observed silicate features are generally well explained by clumpy and smooth torus models. We report the detection of the 6 μm dirty water ice band (i.e., a mix of water and other molecules such as CO and CO2) at subarcsecond scales (∼0.26″ at 6 μm; inner ∼50 pc) in a sample of local AGN with different levels of nuclear obscuration in the range log NHX-Ray (cm−2)∼22 − 25. We find good correlation between the 6 μm water ice optical depths and NHX-Ray. This result indicates that the water ice absorption might be a reliable tracer of the nuclear intrinsic obscuration in AGN. The weak water ice absorption in less obscured AGN (log NHX-ray (cm−2)≲23.0 cm−2) might be related to the hotter dust temperature (> TsubH2O ∼ 110 K) expected to be reached in the outer layers of the torus due to their more inhomogeneous medium. Our results suggest it might be necessary to include the molecular content, such as H2O, aliphatic hydrocarbons (CH−), and more complex polycyclic aromatic hydrocarbon (PAH) molecules, in torus models to better constrain key parameters such as the torus covering factor (i.e., nuclear obscuration).

Future Paths in Cryogenic Single-Molecule Fluorescence Spectroscopy.

In the last three decades, cryogenic single-molecule fluorescence spectroscopy has provided average-free understanding of the photophysics and of fundamental interactions at molecular scales. Furthermore, they propose original pathways and applications in the treatment and storage of quantum information. The ultranarrow lifetime-limited zero-phonon line acts as an excellent sensor to local perturbations caused either by intrinsic dynamical degrees of freedom, or by external perturbations, such as those caused by electric fields, elastic and acoustic deformations, or light-induced dynamics. Single aromatic hydrocarbon molecules, being sensitive to nanoscale probing at nanometer scales, are potential miniaturized platforms for integrated quantum photonics. In this Perspective, we look back at some of the past advances in cryogenic optical microscopy and propose some perspectives for future development.

Deconvoluting the Role of Electrolyte pH, Structural Sensitivity, and Electric Field Effects on the Electrochemical Hydrogenation of Phenol

Traditional thermochemical hydrogenation (TCH) methods that are used in the U.S. chemical and petroleum industries to produce value-added fuels are highly energy intensive. To achieve hydrogenation, they require high temperature and pressure, along with an external source of hydrogen that usually comes from steam methane reformation. Electrochemical hydrogenation (ECH) is an attractive alternative that replaces the thermal driving force with an applied electrical potential, allowing ECH to operate near ambient conditions. The participating protons come from the aqueous electrolyte solution rather than externally produced hydrogen. These features of ECH lower its energy demand compared to TCH and result in less greenhouse gas emissions. ECH is also promising for the processing of biomass feedstocks and could be powered directly by renewable energy, further minimizing the environmental impact.The addition of an aqueous electrolyte and electric field means that insights from TCH should not be directly translated to ECH systems, however, this is often the case in the literature. Fundamental studies on ECH of aromatic hydrocarbons (AHs) are necessary to address current limitations including: competition with the hydrogen evolution reaction (HER) resulting in lower faradaic efficiency, low rates compared to TCH, and little control over selectivity and degree of hydrogenation. For instance, the role of electrolyte pH on phenol ECH remains poorly understood. While some groups have reported negligible phenol turnover rates in electrolytes of pH 10 and above on Pt/C and Pd/C catalysts [1], Song et al. have shown that turnover rates and efficiency are highest on Rh/C at pH 10 [2]. Yet, the idea that low pH (3-5) is best has persisted and the source of the pH dependence remains unknown.In this work we use phenol as a simple representative AH for lignocellulosic bio-oil. We have shown with rotating disk electrode voltammetry that the presence of phenol in electrolytes of pH ~10 enhances HER rates on Pt, Pd, and Au catalysts. Considering that the pKa of phenol is also 10.0, we propose that interfacial phenol molecules channel protons to the catalyst surface by way of facile proton dissociation/reassociation, lowering the barrier for adsorbed H formation in alkaline electrolytes. While this may explain, in part, the low phenol turnover rates observed at higher pH, we further investigate why the opposite is observed on Rh/C catalysts. The role of atomic surface structure is also critical to the adsorption geometry and coverage of AHs. We use well-defined, low-index Pt single crystals to identify the true structural sensitivity for the ECH of AHs. We show with select stepped single crystal surfaces that there is a synergetic role between terrace width/step density that defines activity, balancing coverage of AH molecules, formation of surface adsorbed H, and transfer of that H to AH reactants. We use a low-volume, membrane-separated flow cell for chrono-amperometry followed by product analysis to correlate pH, structural sensitivity, and applied potential to phenol ECH rates and faradaic efficiency. With an understanding of the role of atomic surface structure and the true source of pH dependence, we propose strategies for enhancing phenol turnover rates at lower overpotentials, improving faradaic efficiency, and controlling selectivity.

Application of Sonotriboluminescence to Determine Arene Molecules in Hydrocarbons

The sonotriboluminescence of suspensions of terbium(III) and europium(III) sulfates in decane without and in the presence of benzene, toluene and p-xylene was studied. The choice of crystals of these lanthanides is due to the fact that they have intense luminescence during mechanical action, and also do not dissolve in hydrocarbon solvents. During ultrasonic exposure to suspensions in pure alkanes, bands of Ln3+ ions and N2 in the UV region are recorded in the luminescence spectrum. When aromatic hydrocarbon molecules are added, bands of benzene, toluene and p-xylene molecules, coinciding with their photoluminescence spectra, are recorded in the sonotriboluminescence spectra in the UV region. The high sensitivity of the luminescence of suspensions to arene additives made it possible to obtain the dependence of the characteristic fluorescence of arene molecules in the sonotriboluminescence spectra on their concentration in suspensions. The limits of detection of benzene, toluene and p-xylene in the composition of this suspension were established. The lower limits of detection from the sonotriboluminescence spectra for xylene, toluene and benzene are 0.1, 3 and 50 ppmv, respectively. Fluorescence bands of these molecules were also recorded in the sonotriboluminescence spectra of suspensions in commercial dodecane and heptane with additives of commercial gasoline (up to 1%). The results obtained can be used for luminescent detection of aromatic compounds in saturated hydrocarbons.

Observing π-Au Interaction between Aromatic Molecules and Single Au Nanodimers with a Subnanometer Gap by SERS.

Interface interaction between aromatic molecules and noble metals plays a prominent role in fundamental science and technological applications. However, probing π-metal interactions under ambient conditions remains challenging, as it requires characterization techniques to have high sensitivity and molecular specificity without any restrictions on the sample. Herein, the interactions between polycyclic aromatic hydrocarbon (PAH) molecules and Au nanodimers with a subnanometer gap are investigated by surface-enhanced Raman spectroscopy (SERS). A cleaner and stronger plasmonic field of subnanometer gap Au nanodimer structures was constructed through solvent extraction. High sensitivity and strong π-Au interaction between PAHs and Au nanodimers are observed. Additionally, the density functional theory calculation confirmed the interactions of PAHs physically absorbed on the Au surface; the binding energy and differential charge further theoretically indicated the correlation between the sensitivity and the number of PAH rings, which is consistent with SERS experimental results. This work provides a new method to understand the interactions between aromatic molecules and noble metal surfaces in an ambient environment, also paving the way for designing the interfaces in the fields of catalysis, sensors, and molecular electronics.

Enhanced photocatalytic degradation of polycyclic aromatic hydrocarbon by graphitic carbonitride-nickel (g–C3N4–Ni) nanocomposite

The objective of the present study is to synthesize g-C3N4–Ni nanocomposites composed of graphitic carbon nitride and magnetic nickel nanoparticles for benzopyrene degradation, which is one of the most potent polycyclic aromatic hydrocarbons (PAH) molecules. The concocted g-C3N4–Ni nanocomposites contained confined nanospheres with a mean particle dimension of 22 nm. Batch adsorption studies revealed that a rise in adsorbent dosage elevates benzopyrene degradation percentage in both water and soil samples with respect to time. The increase in the benzopyrene concentration did not have much influence on the degradation efficiency, and hence, the minimal concentration of PAH molecule is essential for the effective adsorption by g-C3N4–Ni nanocomposites. The rise in pH tends to increase the degradation of Benzopyrene till 3 h of the incubation period, and beyond 3 h, the degradation percentage declines. With regard to the effect of light source, UV light has been shown to accelerate the degradation of benzopyrene by g-C3N4–Ni nanocomposites than sunlight. The adsorption kinetic and isotherm investigations have proven that the Pseudo-second order kinetic model and Freundlich isotherm model were appropriate for our study. Thus, the g-C3N4–Ni nanocomposites were found to be efficient as a photocatalyst for the adsorption of benzopyrene from environmental samples.

Aliphatics and Aromatics in the Universe: The Pre-JWST Era

The so-called “unidentified infrared emission” (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs often have an aliphatic component (e.g., aliphatic sidegroups like methyl –CH3 may be attached as functional groups to PAHs) as revealed by the detection in many UIE sources of the aliphatic C–H stretching feature at 3.4 μm. With its unprecedented sensitivity and spatial resolution, and high spectral resolution, the James Webb Space Telescope (JWST) holds great promise for revolutionizing the studies of aliphatics and aromatics in the Universe. To facilitate analyzing JWST observations, we present a theoretical framework for determining the aliphatic fractions (η ali) of PAHs (the fractions of C atoms in aliphatic units) from the emission intensity ratios of the 3.4 μm aliphatic C–H feature to the 3.3 μm aromatic C–H feature. To demonstrate the effectiveness of this framework, we compile the 3.3 and 3.4 μm UIE data obtained in the pre-JWST era for an as-complete-as-possible sample, and then apply the framework to these pre-JWST data. We derive a median aliphatic fraction of 〈η ali〉 ≈ 5.4%, and find that the aliphatic fractions are the highest in protoplanetary nebulae illuminated by cool stars lacking ultraviolet radiation. Nevertheless, the “hardness” of stellar photons is not the only factor affecting the PAH aliphaticity, and other factors such as the starlight intensity may also play an important role.

(Invited) Optical Investigation of Single Nanographenes

Carbon based light emitters ranging from small organic molecules to carbon nanotubes have been subject of a great attention in the framework of diverse applications such as optoelectronics, bio-imaging, and quantum technologies. In this context, graphene quantum dots (GQD) whose size is between that of small polycyclic aromatic hydrocarbon molecules and of carbon nanotubes, have important assets. In particular the complete control of the structure allowed by their synthesis through bottom-up chemistry opens the way to a wide customization of their electronic, optical, and spin properties [1-3].The full benefit from these opportunities requires addressing GQD’s intrinsic photophysical properties. To do so, single molecule photoluminescence experiment is a powerful tool [4-6]. Nevertheless, until now, GQDs faced a problem of solubility that has complexified both the study of their intrinsic properties and their use for applications. In this presentation, we will report on the study of new structures that show a quasi-perfect solubility. We will show how this breakthrough allows us studying in depth their photophysics. Finally, we will see that the theoretical predictions of the evolution of the electronic properties of the GQDs with their structure are fully confirmed by the experiments.[1] M. G. Debije, J. Am. Chem. Soc. 2004, 126, 4641[2] X. Yan, X. Cui, and L.-s. Li, J. Am. Chem. Soc. 2010 132, 5944[3] A. Konishi et al, J. Am. Chem. Soc. 2010, 132, 11021[4] S. Zhao et al, Nature Communications, 2018, 9, 3470[5] T. Liu et al, Nanoscale, 14, 3826 – 3833 (2022)[6] T. Liu et al, Journal of Chemical Physics 156, 104302 (2022)[7] D. Medina-Lopez et al, in preparation

Deuterated Polycyclic Aromatic Hydrocarbons in the Interstellar Medium: The Aliphatic C–D Band Strengths

Abstract Deuterium (D) was exclusively generated in the Big Bang, and the standard Big Bang nucleosynthesis (BBN) model predicts a primordial abundance of D/H ≈ 26 parts per million (ppm). As the Galaxy evolves, D/H gradually decreases because of astration. The Galactic chemical evolution (GCE) model predicts a present-day abundance of D/H ≳ 20 ppm. However, observations of the local interstellar medium have revealed that the gas-phase interstellar D/H varies considerably from one region to another and has a median abundance of D/H ≈ 13 ppm, substantially lower than predicted from the BBN and GCE models. It has been suggested that the missing D atoms of D/H ≈ 7 ppm could have been locked up in deuterated polycyclic aromatic hydrocarbon (PAH) molecules. However, we have previously demonstrated that PAHs with aromatic C–D units are insufficient to account for the missing D. Here we explore if PAHs with aliphatic C–D units could be a reservoir of D. We perform quantum chemical computations of the vibrational spectra of superdeuterated PAHs (in which one D and one H share one C atom) and PAHs to which a D-substituted methyl group is attached, and derive the band strengths of the aliphatic C–D stretch (A 4.65). By applying the computationally derived A 4.65 to the observed aliphatic C–D emission at ∼4.6–4.8 μm, we find that PAHs with aliphatic C–D units could have tied up a substantial amount of D/H and marginally account for the missing D. The possible routes for generating PAHs with aliphatic C–D units are also discussed.

Polycyclic aromatic hydrocarbon molecules and the 2175Å interstellar extinction bump

ABSTRACT The exact nature of the 2175$\mathring{\rm A}$ extinction bump, the strongest spectroscopic absorption feature superimposed on the interstellar extinction curve, remains unknown ever since its discovery in 1965. Popular candidate carriers for the extinction bump include nano-sized graphitic grains and polycyclic aromatic hydrocarbon (PAH) molecules. To quantitatively evaluate PAHs as a possible carrier, we perform quantum chemical computations for the electronic transitions of 30 compact, pericondensed PAH molecules and their cations as well as anions with a wide range of sizes from 16 to 96 C atoms, and a mean size of 43 C atoms. It is found that a mixture of such PAHs, which individually exhibit sharp absorption features, show a smooth and broad absorption band that resembles the 2175$\mathring{\rm A}$ interstellar extinction bump. Arising from π* ← π transitions, the width and intensity of the absorption bump for otherwise randomly selected and uniformly weighted PAH mixtures, do not vary much with PAH sizes and charge states, whereas the position somewhat shifts to longer wavelengths as PAH size increases. While the computed bump position, with the computational uncertainty taken into account, appears to agree with that of the interstellar extinction bump, the computed width is considerably broader than the interstellar bump if the molecules are uniformly weighted. It appears that, to account for the observed bump width, one has to resort to PAH species of specific sizes and structures.