Loss Of Hydrogen Atom Research Articles

Direct detection of diphenylamino radical formed by oxidation of diphenylamine using atmospheric pressure chemical ionization mass spectrometry.

Diphenylamine (DPAH) and its derivatives have been widely used as antioxidants. Its antioxidation behaviors are started with the formation of diphenylamino radical (DPA• ) by loss of hydrogen atom through reaction with oxygen or ozone. DPAH was oxidized by ozonation to produce DPA• and DPA• was directly detected using atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The influence of oxidation time on generation of DPA• and consumption of DPAH was also investigated. Experiments were performed using a home-made ozone bubbling apparatus for oxidation of DPAH. DPAH solution (1000 ppm) in acetone was stirred during the ozonation. The oxidized sample was diluted 100-fold and analyzed using APCI-MS. Structures and energies of DPAH, DPA• and detected ions were obtained using electronic structure calculations with Spartan 10 and Gaussian 09. DPA• was detected in positive APCI-MS in the form of DPAH•+ by proton transfer reaction with protonated acetone. Formation of DPAH•+ from DPA• was more favorable than that of [DPAH + H]+ from DPAH and it was also much more favorable than that of DPA+ from DPA• . By increasing the oxidation time, the relative abundance of DPAH•+ was increased whereas that of [DPAH + H]+ was notably decreased. Existence of DPA• was directly analyzed using APCI-MS. DPAH and DPA• were differently detected as [DPAH + H]+ and DPAH•+ , respectively. Direct APCI-MS analysis is a suitable technique for identification and quantitation of DPA• .

Characterization of sp2/sp3 hybridization ratios of hydrogenated amorphous carbon films deposited in C2H2 inductively coupled plasmas

Hydrogenated amorphous carbon (a-C:H) films were deposited using inductively coupled C 2 H 2 plasma, and the effect of process parameters on the sp 2 /sp 3 hybridization ratio of the films was investigated. The sp 2 /sp 3 ratio was deduced from the intensity ratios of the D and G peaks ( I D /I G ) observed in Raman spectra . The ion density in the C 2 H 2 plasma was determined using an ion probe, and the relative density of CH and H radicals was quantified using optical actinometry. A high I D /I G ratio was observed at high substrate temperatures, and the high sp 2 /sp 3 ratio is attributed to the loss of hydrogen atoms at high temperatures. A high I D /I G ratio was also observed with high plasma power and low pressure. The I D /I G ratio of the a-C:H films increased with increasing ion density in the C 2 H 2 plasmas generated under various conditions, but decreased with the relative density of CH radicals. Ions remove hydrogen atoms from a-C:H films, and CH radicals introduce hydrogen atoms into a-C:H films. The etching resistance of a-C:H films was also investigated, wherein the etch rates of the a-C:H films decreased by 83.3% in the CF 4 plasma and by 70.2% in the O 2 plasma when the sp 2 /sp 3 ratio was increased from 0.97 to 1.62. • The effects of ions and CH radicals were investigated on sp 2 /sp 3 ratios of a-C:H. • Ions in C 2 H 2 plasma make a-C:H films sp 2 -rich because ions remove H atoms in films. • CH radicals make more sp 3 structure in a-C:H due to incorporation of H atoms

Directed Gas-Phase Formation of Aminosilylene (HSiNH2; X1A'): The Simplest Silicon Analogue of an Aminocarbene, under Single-Collision Conditions.

The aminosilylene molecule (HSiNH2, X1A')-the simplest representative of an unsaturated nitrogen-silylene-has been formed under single collision conditions via the gas phase elementary reaction involving the silylidyne radical (SiH) and ammonia (NH3). The reaction is initiated by the barrierless addition of the silylidyne radical to the nonbonding electron pair of nitrogen forming an HSiNH3 collision complex, which then undergoes unimolecular decomposition to aminosilylene (HSiNH2) via atomic hydrogen loss from the nitrogen atom. Compared to the isovalent aminomethylene carbene (HCNH2, X1A'), by replacing a single carbon atom with silicon, a profound effect on the stability and chemical bonding of the isovalent methanimine (H2CNH)-aminomethylene (HNCH2) and aminosilylene (HSiNH2)-silanimine (H2SiNH) isomer pairs is shown; i.e., thermodynamical stabilities of the carbene versus silylene are reversed by 220 kJ mol-1. Hence, the isovalency of the main group XIV element silicon was found to exhibit little similarities with the atomic carbon revealing a remarkable effect not only on the reactivity but also on the thermochemistry and chemical bonding.

Recent Advances in Minisci-type Reactions and Applications in Organic Synthesis

Minisci-type reactions have been widely known as reactions that involve the addition of carbon-centered radicals to basic heteroarenes followed by formal hydrogen atom loss. While the originally developed protocols for radical generation remain in active use today, in recent years, the new array of radical generation strategies have allowed the use of a wider variety of radical precursors that often operate under milder and more benign conditions. New transformations based on free radical reactivity are now available to a synthetic chemist, to utilize a Minisci-type reaction. Radical-generation methods based on photoredox catalysis and electrochemistry, which utilize thermal cleavage or the in situ generation of reactive radical precursors, have become popular approaches. Our review will cover the remarkable literature that has been reported on this topic in recent 5 years, from 2015-01 to 2020-01, in an attempt to provide guidance to the synthetic chemist on both the challenges that need to be overcome and the applications in organic synthesis.

Adhesion between asphalt molecules and acid aggregates under extreme temperature: A ReaxFF reactive molecular dynamics study

In this paper, reactive molecular dynamics is used to investigate the adhesion between asphalt molecules and aggregates, and explore the mechanism of action between asphalt and aggregates. Different asphalt molecules, system temperatures and aging of asphalt are considered. Through numerical simulation, it was found that there are physical (van der Waals force) and chemical interactions between the aggregates and the asphaltene molecules containing hydrogen atoms. The new bond is generated through the chemical reaction, which provides strong bonding force to enhance the adhesion of the interface. Other types of molecules and aggregates are only combined through physical attraction, and the bonding force is weak. In addition, the aging of the asphalt causes the loss of hydrogen atoms, so the adhesion between the asphalt and the aggregate is weakened. In summary, numerical simulation results provided a reference for the research and production of asphalt materials with better adhesion properties.

Thermochemistry, Bond Energies and Internal Rotor Potentials of Acetic Acid Hydrazide, Acetamide, N-Methyl Acetamide (NMA) and Radicals

Structures, thermochemical properties, bond energies, and internal rotation potentials of acetic acid hydrazide (CH3CONHNH2), acetamide (CH3CONH2), and N-methyl acetamide (CH3CONHCH3), and their radicals corresponding to the loss of hydrogen atom, have been studied. Gas-phase standard enthalpies of formation and bond energies were calculated using the DFT methods B3LYP/6-31G(d,p), B3LYP/6-31G(2d,2p) and the composite CBS-QB3 methods employing a series of work reactions further to improve the accuracy of the ΔHf°(298 K). Molecular structures, vibration frequencies, and internal rotor potentials were calculated at the DFT level. The parent molecules’ standard formation enthalpies of CH3–C=ONHNH2, CH3–C=ONH2, and CH3–C=ONHCH3 were evaluated as −27.08, −57.40, and −56.48 kcal mol−1, respectively, from the CBS–QB3 calculations. Structures, internal rotor potentials, and C–H and N–H bond dissociation energies are reported. The DFT and the CBS-QB3 enthalpy values show close agreement, and this accord is attributed to the use of isodesmic work reactions for the analysis. The agreement also suggests this combination of the B3LYP/work reaction approach is acceptable for larger molecules. Internal rotor potentials for the amides are high, ranging from 16 to 22 kcal mol−1.

Direct Production of CH(A2Δ) Radical from Intense Femtosecond Near-IR Laser Pulses.

CH(A2Δ) radical formation was observed in bromoform and methanol vapor in argon plasma with near-infrared femtosecond laser pulses (43 fs, 1030 nm, 100 kHz, 250 μJ/pulse). The beam was focused with an achromatic lens, creating very high intensity in the plasma that caused Coulomb explosion (calculated intensity was ∼1.1 × 1016 W/cm2 in the focal point). The emitted fluorescence light was measured with high spectral (1-10 cm-1) and temporal resolution (5 ns) with an FT-Vis spectrometer. The step-scan technique allowed the reconstruction of the time-resolved fluorescence spectra from CH(A-X) emission. The emission from atomic lines such as H, Br, C, and O was observed and also from C+ cations and CH and C2 radicals. This indicates that in a significant portion of these organic molecules, all chemical bonds were cleaved in the Coulomb explosion. For both organics, the peak maximum of the CH(A) emission occurred at about 10 ns after excitation by the femtosecond pulse. After the maximum, a rapid emission decay was observed in the case of bromoform (monoexponential decay, t = 10 ns). The fluorescence decay was biexponential when methanol was used as the source for CH(A) generation. It can be assumed that CH(A) generation involved a fast and a slower path with some secondary reactions via the stepwise loss of hydrogen atoms from the CH3 group. The time constants were t1 = 7.8-8.3 ns and t2 = 78-82 ns for the fast and slow components, respectively, and very similar values were obtained at 10 and 25 mbar total pressures. However, in the case of bromoform, the C-Br bonds are significantly weaker; therefore, these atoms can be removed even in a single step via multiphoton absorption. The rotational temperature of CH(A) radicals generated from methanol decreased rapidly in the 30-55 ns time period from 2770 ± 80 to 1530 ± 50 K. The vibrational temperature increased from 3530 ± 450 to 9810 ± 760 K in the 30-80 ns time period and then started to decrease (the average temperatures were Trot = 910 ± 20 K and Tvib = 7490 ± 340 K at 100 ns). This initial increase of Tvib is thought to be the result of electron collision with the CH radicals. The high temperatures of the fragment may indicate the roaming reaction associated with the Coulomb explosion of the parent molecule. We demonstrated that CH(A) radicals can be produced from both organic compounds, and the step-scan technique is ideal for the characterization of their time-resolved spectra using the 100 kHz high repetition rate near-infrared femtosecond laser pulses. The FT/UV-vis step-scan technique can detect neutral species directly with high spectral and time resolution, thus it is a complementary technique to the experiments utilizing ion detection schemes, such as velocity map imaging.

Ground and Excited States of Gas-Phase DNA Nucleobase Cation-Radicals. A UV-vis Photodisociation Action Spectroscopy and Computational Study of Adenine and 9-Methyladenine.

Cation radicals of adenine (A•+) and 9-methyladenine (MA•+) were generated in the gas phase by collision-induced intramolecular electron transfer in copper-terpyridine-nucleobase ternary complexes and characterized by collision-induced dissociation (CID) mass spectra and UV-vis photodissociation action spectroscopy in the 210-700 nm wavelength region. The action spectra of both A•+ and MA•+ displayed characteristic absorption bands in the near-UV and visible regions. Another tautomer of A•+ was generated as a minor product by multistep CID of protonated 9-(2-bromoethyl)adenine. Structure analysis by density functional theory and coupled-clusters ab initio calculations pointed to the canonical 9-H-tautomer Ad1•+ as the global energy minimum of adenine cation radicals. The canonical tautomer MA1•+ was also calculated to be a low-energy structure among methyladenine cation radicals. However, two new noncanonical tautomers were found to be energetically comparable to MA1•+. Vibronic absorption spectra were calculated for several tautomers of A•+ and MA•+ and benchmarked on equation-of-motion coupled-clusters excited-state calculations. Analysis of the vibronic absorption spectra of A•+ tautomers pointed to the canonical tautomer Ad1•+ as providing the best match with the action spectrum. Likewise, the canonical tautomer MA1•+ was the unequivocal best match for the MA•+ ion generated in the gas phase. According to potential-energy mapping, MA1•+ was separated from energetically favorable noncanonical cation radicals by a high-energy barrier that was calculated to be above the dissociation threshold for loss of a methyl hydrogen atom, thus preventing isomerization. Structures and energetics of all four DNA nucleobase cation radicals are compared and discussed.

Photolysis-induced scrambling of PAHs as a mechanism for deuterium storage

Aims. We investigate the possible role of polycyclic aromatic hydrocarbons (PAHs) as a sink for deuterium in the interstellar medium (ISM) and study UV photolysis as a potential underlying chemical process in the variations of the deuterium fractionation in the ISM. Methods. The UV photo-induced fragmentation of various isotopologs of deuterium-enriched, protonated anthracene and phenanthrene ions (both C14H10 isomers) was recorded in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer. Infrared multiple photon dissociation spectroscopy using the Free-Electron Laser for Infrared eXperiments was applied to provide IR spectra. Infrared spectra calculated using density functional theory were compared to the experimental data to identify the isomers present in the experiment. Transition-state energies and reaction rates were also calculated and related to the experimentally observed fragmentation product abundances. Results. The photofragmentation mass spectra for both UV and IRMPD photolysis only show the loss of atomic hydrogen from [D − C14H10]+, whereas [H − C14D10]+ shows a strong preference for the elimination of deuterium. Transition state calculations reveal facile 1,2-H and -D shift reactions, with associated energy barriers lower than the energy supplied by the photo-excitation process. Together with confirmation of the ground-state structures via the IR spectra, we determined that the photolytic processes of the two different PAHs are largely governed by scrambling where the H and the D atoms relocate between different peripheral C atoms. The ∼0.1 eV difference in zero-point energy between C–H and C–D bonds ultimately leads to faster H scrambling than D scrambling, and increased H atom loss compared to D atom loss. Conclusions. We conclude that scrambling is common in PAH cations under UV radiation. Upon photoexcitation of deuterium-enriched PAHs, the scrambling results in a higher probability for the aliphatic D atom to migrate to a strongly bound aromatic site, protecting it from elimination. We speculate that this could lead to increased deuteration as a PAH moves towards more exposed interstellar environments. Also, large, compact PAHs with an aliphatic C–HD group on solo sites might be responsible for the majority of aliphatic C–D stretching bands seen in astronomical spectra. An accurate photochemical model of PAHs that considers deuterium scrambling is needed to study this further.

Decomposition of Copper Formate Clusters: Insight into Elementary Steps of Calcination and Carbon Dioxide Activation.

The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II)n(HCO2)2n+1 −, n≤8. In combination with quantum chemical calculations and reactivity measurements using oxygen, elementary steps of the decomposition of copper formate are characterized, which play a key role during calcination as well as for the function of copper hydride based catalysts. The decomposition of larger clusters (n >2) takes place exclusively by the sequential loss of neutral copper formate units Cu(II)(HCO2)2 or Cu(II)2(HCO2)4, leading to clusters with n=1 or n=2. Only for these small clusters, redox reactions are observed as discussed in detail previously, including the formation of formic acid or loss of hydrogen atoms, leading to a variety of Cu(I) complexes. The stoichiometric monovalent copper formate clusters Cu(I)m(HCO2)m+1 −, (m=1,2) decompose exclusively by decarboxylation, leading towards copper hydrides in oxidation state +I. Copper oxide centers are obtained via reactions of molecular oxygen with copper hydride centers, species containing carbon dioxide radical anions as ligands or a Cu(0) center. However, stoichiometric copper(I) and copper(II) formate Cu(I)(HCO2)2 − and Cu(II)(HCO2)3 −, respectively, is unreactive towards oxygen.

Gas-Phase Formation of 1-Methylcyclopropene and 3-Methylcyclopropene via the Reaction of the Methylidyne Radical (CH; X2Π) with Propylene (CH3CHCH2; X1A').

The crossed molecular beam reactions of the methylidyne radical (CH; X2Π) with propylene (CH3CHCH2; X1A') along with (partially) substituted reactants were conducted at collision energies of 19.3 kJ mol-1. Combining our experimental data with ab initio electronic structure and statistical calculations, the methylidyne radical is revealed to add barrierlessly to the carbon-carbon double bond of propylene reactant resulting in a cyclic doublet C4H7 intermediate with a lifetime longer than its rotation period. These adducts undergo a nonstatistical unimolecular decomposition via atomic hydrogen loss through tight exit transition states forming the cyclic products 1-methylcyclopropene and 3-methylcyclopropene with overall reaction exoergicities of 168 ± 25 kJ mol-1. These C4H6 isomers are predicted to exist even in low-temperature environments such as cold molecular clouds like TMC-1, since the reaction is barrierless and exoergic, all transition states are below the energy of the separated reactants, and both the methylidyne radical (CH; X2Π) and propylene reactant were detected in cold molecular clouds such as TMC-1.

Sensitive β-substituted aliphatic Ile/Val-Xxx and aromatic Phe/Tyr/His-Xxx residues to form [a]+ ions in high energy CID of peptides

Residue-specific cleavages resulting in the formation of [a]+ ions of peptides have been examined using 20 keV high-energy (high-E) collision-induced dissociation (CID) with a tandem time-of-flight (TOF/TOF) instrument. High-E CID resulted in relatively sensitive cleavage at the Cα-C bond of β-substituted aliphatic Val/Ile-Xxx and aromatic Phe/Tyr/His-Xxx residues when an Arg residue was located on the N-terminal side. The sensitive aromatic Phe/Tyr/His residues and insensitive Gly residue in high-E CID are similar to other methods, such as ultraviolet photodissociation (UVPD) of [M+H]+, low-E CID of [M].+ and MALDI-ISD with a hydrogen-abstracting matrix. The properties of the Val/Ile residues are not necessarily common to the same methods. The high-sensitivity of Val/Ile and Phe/Tyr/His residues to high-E CID may be due to high-energy single collision between target gas and the bulky sidechains of these residues. It is suggested that from high-E CID and MALDI-ISD experiments the formation of [a]+ ions is essentially connected with the loss of atomic hydrogen from protonated peptides [M+H]+, and that high-E CID results in the loss of hydrogen from the backbone amide nitrogen rather than the site of the β-carbon of sidechains.

Recent Advances in Minisci-Type Reactions.

Reactions that involve the addition of carbon-centered radicals to basic heteroarenes, followed by formal hydrogen atom loss, have become widely known as Minisci-type reactions. First developed into a useful synthetic tool in the late 1960s by Minisci, this reaction type has been in constant use over the last half century by chemists seeking to functionalize heterocycles in a rapid and direct manner, avoiding the need for de novo heterocycle synthesis. Whilst the originally developed protocols for radical generation remain in active use today, they have been joined in recent years by a new array of radical generation strategies that allow use of a wider variety of radical precursors that often operate under milder and more benign conditions. The recent surge of interest in new transformations based on free radical reactivity has meant that numerous choices are now available to a synthetic chemist looking to utilize a Minisci-type reaction. Radical-generation methods based on photoredox catalysis and electrochemistry have joined approaches which utilize thermal cleavage or the in situ generation of reactive radical precursors. This review will cover the remarkably large body of literature that has appeared on this topic over the last decade in an attempt to provide guidance to the synthetic chemist, as well as a perspective on both the challenges that have been overcome and those that still remain. As well as the logical classification of advances based on the nature of the radical precursor, with which most advances have been concerned, recent advances in control of various selectivity aspects associated with Minisci-type reactions will also be discussed.

Elucidating the Chemical Dynamics of the Elementary Reactions of the 1-Propynyl Radical (CH3CC; X2A1) with Methylacetylene (H3CCCH; X1A1) and Allene (H2CCCH2; X1A1).

The reactions of the 1-propynyl radical (CH3CC; X2A1) with two C3H4 isomers, methylacetylene (H3CCCH; X1A1) and allene (H2CCCH2; X1A1), along with their (partially) deuterated counterparts were explored at collision energies of 37 kJ mol-1, exploiting crossed molecular beams to unravel the chemical reaction dynamics to synthesize distinct C6H6 isomers under single collision conditions. The forward convolution fitting of the laboratory data along with ab initio and statistical calculations revealed that both reactions have no entrance barrier, proceed via indirect (complex-forming) reaction dynamics involving C6H7 intermediates with life times longer than their rotation period(s), and are initiated by the addition of the 1-propynyl radical with its radical center to the π-electron density of the unsaturated hydrocarbon at the terminal carbon atoms of methylacetylene (C1) and allene (C1/C3). In the methylacetylene system, the initial collision complexes undergo unimolecular decomposition via tight exit transition states by atomic hydrogen loss, forming dimethyldiacetylene (CH3CCCCCH3) and 1-propynylallene (H3CCCHCCCH2) in overall exoergic reactions (123 and 98 kJ mol-1) with a branching ratio of 9.4 ± 0.1; the methyl group of the 1-propynyl reactant acts solely as a spectator. On the other hand, in the allene system, our experimental data exhibit the formation of the fulvene (c-C5H4CH2) isomer via a six-step reaction sequence with two higher energy isomers-hexa-1,2-dien-4-yne (H2CCCHCCCH3) and hexa-1,4-diyne (HCCCH2CCCH3)-also predicted to be formed based on our statistical calculations. The pathway to fulvene advocates that, in the allene-1-propynyl system, the methyl group of the 1-propynyl reactant is actively engaged in the reaction mechanism to form fulvene. Because both reactions are barrierless and exoergic and all transition states are located below the energy of the separated reactants, the hydrogen-deficient C6H6 isomers identified in our investigation are predicted to be synthesized in low-temperature environments, such as in hydrocarbon-rich atmospheres of planets and their moons such as Titan along with cold molecular clouds such as Taurus Molecular Cloud-1.

Dissociative Photoionization of the C7H8 Isomers Cycloheptatriene and Toluene: Looking at Two Sides of the Same Coin Simultaneously.

The dissociation of energy-selected 1,3,5-cycloheptatriene (CHT) and toluene (Tol) cations was investigated by imaging photoelectron photoion coincidence spectroscopy. In the measured energy ranges of 10.30-11.75 eV for CHT and 11.45-12.55 eV for Tol, only the hydrogen atom loss channels open up, leading to C7H7+ from both molecular ions, which are both metastable at the H-loss threshold. Quantum chemical calculations showed that an interconversion of the molecular ions happens below the dissociation threshold. Therefore, a single statistical model was constructed to describe both systems simultaneously. We determined 0 K appearance energies for the tropylium (Tr+) and benzyl (Bz+) fragment ions from CHT to be 9.520 ± 0.060 and 9.738 ± 0.082 eV and that from Tol to be 10.978 ± 0.063 and 11.196 ± 0.080 eV, respectively. Using the experimentally determined benzyl ion appearance energy, its 0 K heat of formation was calculated to be 937.9 ± 7.7 kJ mol-1. Finally, on the basis of this value and the recently determined benzyl ionization energy, we point out discrepancies concerning the benzyl radical thermochemistry.

A combined experimental and computational study on the reaction dynamics of the 1-propynyl radical (CH3CC; X2A1) with ethylene (H2CCH2; X1A1g) and the formation of 1-penten-3-yne (CH2CHCCCH3; X1A').

The crossed molecular beam reactions of the 1-propynyl radical (CH3CC; X2A1) with ethylene (H2CCH2; X1A1g) and ethylene-d4 (D2CCD2; X1A1g) were performed at collision energies of 31 kJ mol-1 under single collision conditions. Combining our laboratory data with ab initio electronic structure and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations, we reveal that the reaction is initiated by the barrierless addition of the 1-propynyl radical to the π-electron density of the unsaturated hydrocarbon of ethylene leading to a doublet C5H7 intermediate(s) with a life time(s) longer than the rotation period(s). The reaction eventually produces 1-penten-3-yne (p1) plus a hydrogen atom with an overall reaction exoergicity of 111 ± 16 kJ mol-1. About 35% of p1 originates from the initial collision complex followed by C-H bond rupture via a tight exit transition state located 22 kJ mol-1 above the separated products. The collision complex (i1) can also undergo a [1,2] hydrogen atom shift to the CH3CHCCCH3 intermediate (i2) prior to a hydrogen atom release; RRKM calculations suggest that this pathway contributes to about 65% of p1. In higher density environments such as in combustion flames and circumstellar envelopes of carbon stars close to the central star, 1-penten-3-yne (p1) may eventually form the cyclopentadiene (c-C5H6) isomer via hydrogen atom assisted isomerization followed by hydrogen abstraction to the cyclopentadienyl radical (c-C5H5) as an important pathway to key precursors to polycyclic aromatic hydrocarbons (PAHs) and to carbonaceous nanoparticles.

How to add a five-membered ring to polycyclic aromatic hydrocarbons (PAHs) - molecular mass growth of the 2-naphthyl radical (C10H7) to benzindenes (C13H10) as a case study.

The three-ring polycyclic aromatic hydrocarbons (PAHs) 3H-benz[e]indene (C13H10) and 1H-benz[f]indene (C13H10) along with their naphthalene-based isomers 2-(prop-2-yn-1-yl)naphthalene (C13H10), 2-(prop-1-yn-1-yl)naphthalene (C13H10), and 2-(propa-1,2-dien-1-yl)naphthalene (C13H10) were formed through a "directed synthesis"via a high temperature chemical micro reactor under combustion-like conditions (1300 ± 35 K) through the reactions of the 2-naphthyl isomer (C10H7˙) with allene (C3H4) and methylacetylene (C3H4). The isomer distributions were probed utilizing tunable vacuum ultraviolet radiation from the Advanced Light Source (ALS) by recording the photoionization efficiency curves at mass-to-charge of m/z = 166 (C13H10) and 167 (13CC12H10) of the products in a supersonic molecular beam. Complemented by electronic structure calculations, our study reveals critical mass growth processes via annulation of a five-membered ring from the reaction between aryl radicals and distinct C3H4 isomers at elevated temperatures as present in combustion processes and in circumstellar envelopes of carbon stars. The underlying reaction mechanisms proceed through the initial addition of the 2-naphthyl radical with its radical center to the π-electron density of the allene and methylacetylene reactants via entrance barriers between 8 and 14 kJ mol-1, followed by isomerization (hydrogen shifts, ring closure), and termination via atomic hydrogen losses accompanied by aromatization. The reaction mechanisms reflect the formation of indene - the prototype PAH carrying a single five- and a single six-membered ring - synthesized through the reaction of the phenyl radical (C6H5˙) with allene and methylacetylene. This leads us to predict that aryl radicals - upon reaction with allene/methylacetylene - may undergo molecular mass growth processes via ring annulation and de facto addition of a five-membered ring to form molecular building blocks essential to transit planar PAHs out of the plane.

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane.

A structural characterization of the products formed in the dissociative electron ionization of adamantane (C10H16) is presented. Molecular structures of product ions are suggested based on multiple‐photon dissociation spectroscopy using the Free Electron Laser for Infrared eXperiments (FELIX) in combination with quantum‐chemical calculations. Product ions are individually isolated in an ion trap tandem mass spectrometer and their action IR spectra are recorded. Atomic hydrogen loss from adamantane yields the 1‐adamantyl isomer. The IR spectrum of the C8H11 + product ion is best reproduced by computed spectra of 2‐ and 4‐protonated meta‐xylene and ortho‐ and para‐protonated ethylbenzenes. The spectrum of the product ion at m/z 93 suggests that it is composed of a mixture of ortho‐protonated toluene, para‐protonated toluene and 1,2‐dihydrotropylium, while the spectrum of the m/z 79 ion is consistent with the benzenium ion. This study thus suggests that adamantane is efficiently converted into aromatic species and astrophysical implications for the interstellar medium are highlighted.

Formation of Covalently Bonded Polycyclic Aromatic Hydrocarbons in the Interstellar Medium

Photo-/ion-induced ionization and dissociation processes are commonly observed for polycyclic aromatic hydrocarbon (PAH) molecules. This work performs theoretical studies of PAHs and their fragments. Molecular dynamics simulations in combination with static quantum chemical calculations reveal that following a single hydrogen atom loss, the fragments, PAH-H, are extremely reactive. They catch a neighbor molecule within picoseconds to form a covalently bonded large molecule regardless of orientations/angles and temperatures. We calculate the infrared spectra of the covalently bonded molecules, which indicate that such species could be the carrier of unidentified infrared emission bands. It also implies that regular PAHs might be less abundant in space than what is expected.

Frontier Orbitals of Dehydrogenated Tetrahydrocurcumin in Water Solvent: A Theoretical Study

We studied two frontier orbitals - the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)- of tetrahydrocurumin (THC) using density-functional theory (DFT) in water solvent. These orbitals were observed in THC molecule without one hydrogen atom (dehydrogenated THC). The loss of hydrogen atom is due to the transfer of the atom from THC molecule toward reactive oxygen species (ROS) (Hydrogen atom transfer –HAT- mechanism). We began our investigation by optimizing dehydrogenated THC at three X-H sites. Then, water solvent was added by using polarized continuum model (PCM) method. This study observed that dehydrogenated THC at two O-H sites has wider gap of HOMO-LUMO compare to C-H site.