Impact of PAH photodissociation on the formation of small hydrocarbons in the Orion Bar and the horsehead PDRs

ABSTRACT We study whether polycyclic aromatic hydrocarbons (PAHs) can be a weighty source of small hydrocarbons in photodissociation regions (PDRs). We modelled the evolution of 20 specific PAH molecules in terms of dehydrogenation and destruction of the carbon skeleton under the physical conditions of two well-studied PDRs, the Orion Bar, and the Horsehead nebula that represent prototypical examples of PDRs irradiated by ‘high’ and ‘low’ ultraviolet radiation field. PAHs are described as microcanonical systems. The acetylene molecule is considered as the main carbonaceous fragment of the PAH dissociation, as it follows from laboratory experiments and theory. We estimated the rates of acetylene production in gas phase chemical reactions and compared them with the rates of the acetylene production through the PAH dissociation. It is found that the latter rates can be higher than the former rates in the Orion Bar at AV < 1 and also at AV > 3.5. In the Horsehead nebula, the chemical reactions provide more acetylene than the PAH dissociation. The produced acetylene participate in the reactions of the formation of small hydrocarbons (C2H, C3H, C3H+, C3H2, C4H). Acetylene production via the PAH destruction may increase the abundances of small hydrocarbons produced in gas phase chemical reactions in the Orion Bar only at AV > 3.5. In the Horsehead nebula, the contribution of PAHs to the abundances of the small hydrocarbons is negligible. We conclude that the PAHs are not a major source of small hydrocarbons in both PDRs except some locations in the Orion Bar.

Association of Cl with C2H2by unified variable-reaction-coordinate and reaction-path variational transition-state theory

Barrierless unimolecular association reactions are prominent in atmospheric and combustion mechanisms but are challenging for both experiment and kinetics theory. A key datum for understanding the pressure dependence of association and dissociation reactions is the high-pressure limit, but this is often available experimentally only by extrapolation. Here we calculate the high-pressure limit for the addition of a chlorine atom to acetylene molecule (Cl + C2H2→C2H2Cl). This reaction has outer and inner transition states in series; the outer transition state is barrierless, and it is necessary to use different theoretical frameworks to treat the two kinds of transition state. Here we study the reaction in the high-pressure limit using multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) at the outer transition state and reaction-path variational transition state theory (RP-VTST) at the inner turning point; then we combine the results with the canonical unified statistical (CUS) theory. The calculations are based on a density functional validated against the W3X-L method, which is based on coupled cluster theory with single, double, and triple excitations and a quasiperturbative treatment of connected quadruple excitations [CCSDT(Q)], and the computed rate constants are in good agreement with some of the experimental results. The chlorovinyl (C2H2Cl) adduct has two isomers that are equilibrium structures of a double-well C≡C–H bending potential. Two procedures are used to calculate the vibrational partition function of chlorovinyl; one treats the two isomers separately and the other solves the anharmonic energy levels of the double well. We use these results to calculate the standard-state free energy and equilibrium constant of the reaction.

Gas Phase Ionization of Toluene: Benzylium Versus Tropylium Pathway

Aim: In this investigation, we used accurate mass high-resolution gas chromatography mass spectrometry to study the gas phase carbocations rearrangements and fragmentation of toluene and halo-toluenes as well as their deuterium labeled compounds. Objective: Accurate mass of selected ions from ionization of toluene and related compounds revealed that the initially formed radical cation C7H8 +. does not rearrange to tropylium radical cation contradicting published literature. Methods: When the toluene radical cation was purely selected, it was found to lose a free radical (hydrogen atom) at collision energies greater than 5 eV and forming benzylium or tropylium cation C7H7 + (m/z = 91), with no other fragmentations. Results: The resulting cation at collision energy greater than 20 eV fragmented by losing acetylene or ethylene or allene molecule to form C5H5 + (m/z = 65), C5H3 + (m/z = 63) or C4H3 + (m/z = 51) respectively. Purely selected C5H5 + cation at collision energy greater than 30 eV lost acetylene molecule and formed C3H3 + (m/z =39). Conclusion: In this investigation toluene, halotoluene and their deuterated derivatives (structural isomers) were found to ionize in the gas phase with isomer retention. Historically, it has been suggested that the seven carbons and hydrogen atoms would become indistinguishable. However, this should be revised in the light of new technologies.

Acetylene in Organic Synthesis: Recent Progress and New Uses

Recent progress in the leading synthetic applications of acetylene is discussed from the prospect of rapid development and novel opportunities. A diversity of reactions involving the acetylene molecule to carry out vinylation processes, cross-coupling reactions, synthesis of substituted alkynes, preparation of heterocycles and the construction of a number of functionalized molecules with different levels of molecular complexity were recently studied. Of particular importance is the utilization of acetylene in the synthesis of pharmaceutical substances and drugs. The increasing interest in acetylene and its involvement in organic transformations highlights a fascinating renaissance of this simplest alkyne molecule.

Synthesis of Monobactams via the Diastereoselective Kinugasa Reaction

The Kinugasa reaction between phthalimidoacetylene and cyclic nitrones derived from l-phenylglycine or l-serine and glyoxylic acid­, catalyzed by copper(I) chloride in the presence of triethylamine, is reported. The acetylene molecule approaches the nitrone exclusively anti to the bulky substituent next to the nitrogen atom to provide the cis-substituted β-lactam ring preferentially. The six-membered oxazinone ring can be easily opened, the phthaloyl residue can be transformed into a Boc protecting group, and substituents at the C-4 carbon atom and the nitrogen atom of the β-lactam ring can be easily removed or transformed into groups suitable for further synthesis of a variety of monobactam structures. Selected synthesized compounds were evaluated for their biological activity, showing interesting properties.

A new rod-shaped BODIPY-acetylene molecule for solution-processed semiconducting microribbons in n-channel organic field-effect transistors

A novel solution-processable BODIPY-based small molecule (BDY-PhAc-BDY) yields highly-crystalline, one-dimensional (1-D) microribbon semiconductors for organic field-effect transistors (OFETs).

Large amplitude motion of the acetylene molecule within acetylene–neon complexes hosted in helium droplets

This work examines how the non-superfluid component of helium droplets hosting a C2H2–Ne complex affects the hindered rotation of C2H2 within the complex.