The formation and destruction of doubly-charged polycyclic aromatic hydrocarbon cations in the interstellar medium

Large polycyclic aromatic hydrocarbons (PAH) have recently been held responsible for certain IR emission bands and visible region diffuse absorption bands observed in the interstellar medium (ISM). A mechanism for the fragmentation and eventual destruction of PAH species in the ISM is suggested. This involves a number of excitation processes that could lead to their double ionization in the ISM. The possibility of fragmentation of the doubly-charged PAHs by Coulomb explosion processes involving rapid direct dissociation or by tunnelling processes is examined in the context of the relevant cosmic timescale and events in the ISM.     

An experimental and modeling study of tetramethyl ethylene pyrolysis with polycyclic aromatic hydrocarbon formation

Iso-olefins, in the C₅–C₈ range can potentially be blended with renewable gasoline fuels to increase their research octane number (RON) and octane sensitivity (S). RON and S increase with the degree of branching in iso-olefins and this is a desirable fuel anti-knock quality in modern spark-ignited direct-injection engines. However, these iso-olefins tend to form larger concentrations of aromatic species leading to the formation of polycyclic aromatic hydrocarbons (PAHs). Thus, it is important to understand the pyrolysis chemistry of these iso-olefins. In this study, a new detailed chemical kinetic mechanism is developed to describe the pyrolysis of tetramethyl ethylene (TME), a symmetric iso-olefin. The mechanism, which includes the formation of PAHs, is validated against species versus temperature (700–1160 K) measurements in a jet-stirred reactor at atmospheric pressure and in a single-pulse shock tube at a pressure of 5 bar in the temperature range 1150–1600 K. Synchrotron vacuum ultraviolet photoionization mass spectrometer (SVUV-PIMS) and gas chromatography (GC) systems were used to quantify the species in the jet-stirred reactor and in the single-pulse shock tube, respectively. The mechanism derives its base and PAH chemistry from the LLNL PAH sub-mechanism. The predictions are accurate for most of the species measured in both facilities. However, there is scope for mechanism improvement by understanding the consumption pathways for some of the intermediate species such as isoprene. The formation of 1, 2, and 3-ring aromatic species such as benzene, toluene, naphthalene and phenanthrene measured experimentally is analyzed using the chemical kinetic mechanism. It is found that the PAH formation chemistry for TME under pyrolysis conditions is driven by both propargyl addition reactions and the HACA mechanism.     

Unimolecular dissociation of hydroxypropyl and propoxy radicals

Unimolecular pressure- and temperature-dependent decomposition rate coefficients of radicals derived from n- and i-propanol by H-atom abstraction are calculated using a time-dependent master equation in the 300–2000 K temperature range. The calculations are based on a C₃H₇O potential energy surface, which was previously tested successfully for the propene + OH reaction. All rate coefficients are obtained with internal consistency with particular attention paid to shallow wells. After minor adjustments very good agreement with the few available experimental results is obtained. Several interesting pathways are uncovered, such as the catalytic dehydration, well-skipping reactions and reactions forming enols. The results of the calculations can be readily used in CHEMKIN simulations or to assess important channels for higher alcohols.     

Relative rate constants for the formation of muonic radicals in liquid aromatic systems

The distribution of muon polarization between different radicals observed in neat p-di-fluorobenzene, aniline and bromobenzene and their binary mixtures with benzene has been measured and is interpreted in terms of relative rate constants for Mu addition. Mu shows the same intramolecular and intermolecular selectivity pattern as the heavier hydrogen isotopes, but its selectivity is smaller.Support by the Swiss National Foundation for Scientific Research, by the Swiss Institute for Nuclear Research (SIN), the Netherlands Organisation for the Advancement of Pure Research (Z.W.O.) and the Foundation for Fundamental Research on Matter (F.O.M.) are gratefully acknowledged.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

The formation of polycyclic aromatic hydrocarbons from the supercritical pyrolysis of 1-methylnaphthalene

In order to better understand the pyrolytic reactions leading to the formation of polycyclic aromatic hydrocarbons (PAH) and carbonaceous solids under supercritical conditions, we have pyrolyzed the model fuel 1-methylnaphthalene (critical temperature, 499 °C; critical pressure, 36 atm) in an isothermal silica-lined stainless-steel reactor coil at 585 °C, 110 atm, and 140 s. Analysis of the reaction products by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection and mass spectrometric detection has led to the identification of 37 individual 2- to 7-ring PAH—fifteen of which have never before been reported as products of 1-methylnaphthalene pyrolysis. The absence, among the reaction products, of single-ring aromatics and acetylene indicates that there is no aromatic ring rupture in this reaction environment, and the structures of each of the 5- to 7-ring PAH products reveal the intactness of the two 2-ring naphthalene units required in their construction. Proposed reaction pathways involving species plentiful in the reaction environment—1-naphthylmethyl radical, methyl radical, 1-methylnaphthalene, naphthalene, and 2-methylnaphthalene—account for the formation of the observed 5- to 7-ring PAH products. These reaction pathways, along with consideration of bond dissociation energies and relative abundances of reactant species, account for the extremely high product selectivity exhibited by the observed product PAH. The detection of seven 8- and 9-ring PAH, each requiring construction from three naphthalene or methylnaphthalene units, provides evidence that the types of reaction mechanisms outlined here—for the combination of two naphthalene entities to form 5- to 7-ring PAH—are also likely to apply to the combination of three and more such entities in the formation of larger-ring-number PAH and eventually carbonaceous solids.     

Blending effect of methanol on the formation of polycyclic aromatic hydrocarbons in the oxidation of toluene

Methanol has been considered as a potential renewable liquid fuel and blending it with gasoline and diesel is an effective way to reduce greenhouse gas emissions from the transport sector. To understand the mixing effect of methanol on the formation of polycyclic aromatic hydrocarbons (PAHs) and oxygenated PAHs (OPAHs), the fuel-rich oxidation of toluene with and without methanol was studied using a flow reactor at atmospheric pressure, temperatures from 1050 to 1350 K, equivalence ratio of 9.0, and residence time of 1.2 s. The blending ratio of methanol was varied as 0% and 50% on a molar basis. Gas chromatograph mass spectrometer was employed to identify and quantify PAHs and OPAHs in gaseous products. A kinetic model on PAH growth up to five ring structures was used to investigate the blending effect on PAH and OPAH formation. Both experiment and modeling showed that PAH and OPAH production at lower temperatures was unexpectedly promoted in toluene/methanol oxidation compared with toluene oxidation, while their production in toluene oxidation was identical with or larger than that in toluene/methanol oxidation at elevated temperatures. In methanol oxidation, no PAHs were produced under the current experimental conditions. Kinetic analysis indicated that high methanol reactivity produced several radicals, such as OH, H, and HO₂, which promoted toluene reactivity at lower temperatures, resulting in the enlargement of PAH and OPAH formation in toluene/methanol oxidation compared to neat toluene oxidation. When the temperature was increased, the effect of methanol blending was diminished based on the kinetic analysis. These results suggest that oxygenated fuels do not necessarily reduce PAH production, but promote it under some conditions.     

The role played by the enthalpy of reactions in the disproportionation of free radicals

A semiempirical model of radical disproportionation was suggested. The reaction was modeled by an intersection of two potential curves describing stretching vibrations of interacting bonds. One of these curves was a parabola (stretching vibration of the attacked bond), and the other, a Morse curve (stretching vibration of the arising bond). Equations describing an increase in the interatomic distance in the reaction center of the transition state of such reactions as a function of the enthalpy of the reaction were obtained. A comparison of the calculation results and experimental data was performed to derive equations that described the rate constant for disproportionation as a function of bond elongation in the transition state and reaction enthalpy. A simple method for calculating interatomic distances in the reaction center of the reactions was suggested. Rate constants for several unstudied radical disproportionation reactions were calculated. The problem of the competition of disproportionation at various reaction centers was considered.     

Spontaneous formation of free radicals in cryochemical reactions of halogenation of hydrocarbons and nanomaterials

A range of issues related to free-radical processes in polymer-monomer systems is considered. Spectral (EPR, IRS) and other physicochemical methods (calorimetry, chromatography, viscometry) are used to demonstrate that the low-temperature treatment of polymers and monomers with halogens (fluorine, chlorine) is accompanied by the spontaneous formation of free radicals. At F₂ and Cl₂ pressures below 100 Torr, the concentration of radicals reaches 10¹⁷–10¹⁹ spin/g, which can be reproduced in the case of radiolysis only by using doses of several hundred (or thousand) kGy. The formation of radicals through the cleavage of chemical bonds (without external energy impact on the system) is discussed in the framework of the model of low-temperature reactions in polymolecular complexes, involving the simultaneous occurrence of endothermic and exothermic steps in one elementary event with an overall exothermic effect. It is shown that the radicals formed can be used to initiate the polymerization of vinyl and acetylene monomers.     

Overtone and combination features of G and D peaks in resonance Raman spectroscopy of the C78H26 polycyclic aromatic hydrocarbon

We have studied the Raman spectra of C₇₈H₂₆, a polycyclic aromatic hydrocarbon with D_2h symmetry point group resembling a longitudinally confined graphene ribbon (or a graphene island) with armchair edge. The experimental spectra recorded with several excitation laser lines have been compared with the results from a theoretical analysis of the resonant Raman response based on density functional theory calculations. Compared to previous investigation the spectra show better signal‐to‐noise ratio, which allows determining previously unresolved weak spectroscopic features. We have extended our analysis to the overtone and combination region (i.e. above 2000 cm⁻¹) demonstrating the presence of signals attributable to 2G, G + D, 2D, D_j + D_k and G + acoustic‐like modes. Moreover, we have measured the temperature dependence of the G peak position, which turns out to show a similar behavior with respect to that of graphene/graphite. Copyright © 2015 John Wiley & Sons, Ltd.     

Selective SERS detection of each polycyclic aromatic hydrocarbon (PAH) in a mixture of five kinds of PAHs

This paper reports the qualitative analysis and quantitative detection of polycyclic aromatic hydrocarbon (PAH) molecules with per‐6‐deoxy‐(6‐thio)‐β‐cyclodextrin (CD‐SH) modified gold nanoparticles (AuNPs) by surface‐enhanced Raman scattering (SERS) spectroscopy. For the selective sensing of PAHs, which are environmental pollutants with very low affinity to metallic surfaces, by SERS, a stable substrate with AuNPs and CD‐SH was utilized by supramolecular interaction. Quantitative detection of each PAH was carried out by SERS on inclusion complexes with different concentrations. From the SERS spectra of a mixture of five different PAHs, we could easily distinguish each PAH by its discriminant peaks. In addition, quantitative analysis of one component in a mixture of five PAHs was also investigated. This sensing platform revealed matching relationship between the host and the guest and the host–guest interaction mechanism. The proposed approach for the selective detection of PAHs holds great potential in the detection of environmental organic pollutants. Copyright © 2010 John Wiley & Sons, Ltd.     

Functionalisation of graphene by edge-halogenation and radical addition using polycyclic aromatic hydrocarbon models: edge electron density-binding energy relationship

Structures and properties of functionalised graphene were investigated using several derivatives of some small polycyclic aromatic hydrocarbons (PAHs) taken as finite size models employing unrestricted density functional theory. The functionalisation reactions included fluorination or chlorination of all the edge carbon sites, addition of H, F or Cl atom, OH or OOH group at the different sites and addition of OH or OOH group at the different sites of the edge-halogenated PAHs. σ-inductive effects of fluorine and chlorine in the edge-fluorinated and edge-chlorinated PAHs, respectively, were found to affect electron density and molecular electrostatic potential (MEP) distributions significantly. σ-holes were located at the MEP surfaces along the CH and CCl bonds of the unmodified and edge-chlorinated PAHs, respectively. The H and F atoms and the OH group were found to add to all the carbon sites of PAHs exothermically, while addition of the Cl atom and the OOH group was found to be exothermic at a few carbon sites and endothermic at the other carbon sites. Enhanced electron densities at the edge carbon sites of the PAHs and binding energies of adducts of H and F atoms and the OH group at these sites were found to be linearly correlated.     

Theoretical evaluation of NMR shifts in polycyclic aromatic hydrocarbons

ABSTRACT

Using computational chemistry methodology, we evaluate the proton magnetic shieldings and the corresponding chemical shifts of 12 polycyclic aromatic hydrocarbons that derive from chrysene, perylene and picene. Due to the large size of the studied compounds, we resort to density functional theory (DFT) and use it together with the B3LYP and the KT1 functionals. After a systematic method and basis set selection study carried out on methane, benzene and anthracene, the DFT(B3LYP) method and the 6-31G*, 6-31G** and 6-311++G** bases are selected to carry out the calculations, because of the efficiency in providing shifts close to the experimental data available. Additionally, we select the DFT(KT1) method together with the aug-pcS-1 basis set, and HF/6-31G* shifts are also calculated. In order to estimate the error in the theoretical results, we take as reference accurate experimental chemical shifts obtained for the molecules under investigation. Extra measurements are needed for this purpose and are included in the present work. The best combination of method and basis set is DFT(B3LYP)/6-31G**, proving to be very efficient in getting shifts close to experiment at a relatively low computational cost, and therefore we recommend it for the evaluation of proton shifts in larger polycyclic aromatic hydrocarbons.     

On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Study of surface and solution properties of gemini-conventional surfactant mixtures and their effects on solubilization of polycyclic aromatic hydrocarbons

The aqueous solubility enhancement of the polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene and pyrene by micellar solutions of single gemini surfactant hexanediyl-1,6-bis(dimethylcetylammonium bromide) (G6) and its mixtures with cationic cetyltrimethylammonium bromide (CTAB), anionic sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and nonioinic polyoxyethylene (20) cetyl ether (Brij 58) have been investigated. Above the cmc, maximum solubilization occurs in the Brij 58 surfactant micelles whereas the solubilization is least in presence of AOT. The PAHs are solubilized synergistically in mixed gemini-conventional surfactant solutions, which is attributed to the formation of mixed micelles, their lower cmc values, and the increase of the solvents' molar solubilization ratios or micellar partition coefficients because of the lower polarity of the mixed micelles.     

The influence of the aromatic character in the gas chromatography elution order: the case of polycyclic aromatic hydrocarbons

A link between the aromatic character of polycyclic aromatic hydrocarbons (PAHs) and gas chromatography (GC) elution order in columns with a polysiloxane backbone in the stationary phase is reported for the first time. The aromatic character was calculated using a method that combines the π-Sextet Rule and the Pauling Ring Bond Orders to allow the establishment of the location and migration of aromatic sextets in PAH structures. One GC column with a polysiloxane-like backbone (Rxi-PAH) and three GC columns with a polysiloxane backbone (DB-5, SE-52 and LC-50) were used for the analysis. According to the results of this study, within an isomer group, PAHs that contain a lower number of rings affected by the aromatic sextets tend to elute earlier than PAHs that contain a higher number of rings affected by the aromatic sextets. The PAHs that follow the calculated elution order are 88% in the Rxi-PAH column, 88% in the DB-5 column, 93% in the SE-52 column and 85% in the LC-50 column. It is expected that future analyses with other aromatic compounds in GC columns with a polysiloxane backbone in the stationary phase will follow a GC elution order that agrees with the aromatic character of the molecules.     

Structural and electronic properties of linear and angular polycyclic aromatic hydrocarbons

The structural and electronic properties of linear and angular polycyclic aromatic hydrocarbons (PAHs) have been studied by ab initio calculations. We show that the HOMO–LUMO gaps of linear and angular PAHs are inversely proportional to their width and length and angular PAHs always exhibit larger HOMO–LUMO gaps than their linear isomers, indicating the relative higher kinetic stability for angular PAHs. The frontier orbitals of HOMO and LUMO are localized at the zigzag edges in linear PAHs, while they are distributed uniformly over the molecules in angular PAHs. These results offer key insight for understanding the size and topology depending effects, which is of great use for experimental syntheses of PAHs with specific electronic properties.     

Single photon infrared emission spectroscopy of the gas phase pyrene cation: support for a polycyclic aromatic hydrocarbon origin of the unidentified infrared emission bands.

We report the first observation of infrared emission from a gaseous ionic polycyclic aromatic hydrocarbon (PAH), the pyrene cation, over the range of wavelengths spanned by the ubiquitous interstellar unidentified infrared emission bands (UIRs). The complete set of pyrene cation IR emissions is observed, with relative intensities consistent with astrophysical observations, supporting the proposal that ionized PAHs are major contributors to the UIR bands. Additionally, unidentified features possibly arising from dehydrogenated PAH species are noted in the spectrum.