A combined crossed molecular beam and theorerical study of the O(3P,1D) + acrylonitrile (CH2CHCN) reactions and implications for combustion and extraterrestrial environments.

Acrylonitrile (CH2CHCN) is ubiquitous in space (molecular clouds, solar-type star forming regions, and circumstellar envelopes) and is also abundant in the upper atmosphere of Titan. The reaction O(3P) + CH2CHCN can be of relevance in the chemistry of the interstellar medium because of the abundance of atomic oxygen. The oxidation of acrylonitrile is also important in combustion as the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including acrylonitrile. Despite its relevance, limited information exists on this reaction. We report a combined experimental and theoretical investigation of the reactions of acrylonitrile with both ground 3P and excited 1D atomic oxygen. From product angular and time-of-flight distributions in crossed molecular beam experiments with mass spectrometric detection at a collision energy, Ec, of 31.4 kJ mol-1, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to interpret the experimental results and elucidate the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have been carried out. Combining the experimental and theoretical results, we conclude that the O(3P) reaction leads to two main product channels: (i) CH2CNH (ketenimine) + CO (dominant with a BF of 0.87 ± 0.05), formed via efficient intersystem crossing from the entrance triplet PES to the underlying singlet PES, and (ii) HCOCHCN + H (minor, with a BF of 0.13 ± 0.05), occurring adiabatically on the triplet PES. Our study suggests the inclusion of this reaction as a possible destruction pathway of CH2CHCN and a possible formation route of CH2CNH in the interstellar medium. The O(1D) + CH2CHCN reaction mainly leads to the formation of CH2CNH + CO adiabatically on the singlet PES. This result can improve models related to the chemistry of interstellar ice and cometary comas, where O(1D) reactions can play a role. Overall, our results are expected to be useful for improving the models of combustion and extraterrestrial environments.

OH(2Π) + C2H4 Reaction: A Combined Crossed Molecular Beam and Theoretical Study.

The reaction between the ground-state hydroxyl radical, OH(2Π), and ethylene, C2H4, has been investigated under single-collision conditions by the crossed molecular beam scattering technique with mass-spectrometric detection and time-of-flight analysis at the collision energy of 50.4 kJ/mol. Electronic structure calculations of the underlying potential energy surface (PES) and statistical Rice-Ramsperger-Kassel-Marcus (RRKM) calculations of product branching fractions on the derived PES for the addition pathway have been performed. The theoretical results indicate a temperature-dependent competition between the anti-/syn-CH2CHOH (vinyl alcohol) + H, CH3CHO (acetaldehyde) + H, and H2CO (formaldehyde) + CH3 product channels. The yield of the H-abstraction channel could not be quantified with the employed methods. The RRKM results predict that under our experimental conditions, the anti- and syn-CH2CHOH + H product channels account for 38% (in similar amounts) of the addition mechanism yield, the H2CO + CH3 channel for ∼58%, while the CH3CHO + H channel is formed in negligible amount (<4%). The implications for combustion and astrochemical environments are discussed.

Reactions O(3P, 1D) + HCCCN(X1Σ+) (Cyanoacetylene): Crossed-Beam and Theoretical Studies and Implications for the Chemistry of Extraterrestrial Environments.

Cyanoacetylene (HCCCN), the first member of the cyanopolyyne family (HCnN, where n = 3, 5, 7, ...), is of particular interest in astrochemistry being ubiquitous in space (molecular clouds, solar-type protostars, protoplanetary disks, circumstellar envelopes, and external galaxies) and also relatively abundant. It is also abundant in the upper atmosphere of Titan and comets. Since oxygen is the third most abundant element in space, after hydrogen and helium, the reaction O + HCCCN can be of relevance in the chemistry of extraterrestrial environments. Despite that, scarce information exists not only on the reactions of oxygen atoms with cyanoacetylene but with nitriles in general. Here, we report on a combined experimental and theoretical investigation of the reactions of cyanoacetylene with both ground 3P and excited 1D atomic oxygen and provide detailed information on the primary reaction products, their branching fractions (BFs), and the overall reaction mechanisms. More specifically, the reactions of O(3P, 1D) with HCCCN(X1Σ+) have been investigated under single-collision conditions by the crossed molecular beams scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy, Ec, of 31.1 kJ/mol. From product angular and time-of-flight distributions, we have identified the primary reaction products and determined their branching fractions (BFs). Theoretical calculations of the relevant triplet and singlet potential energy surfaces (PESs) were performed to assist the interpretation of the experimental results and clarify the reaction mechanism. Adiabatic statistical calculations of product BFs for the decomposition of the main triplet and singlet intermediates have also been carried out. Merging together the experimental and theoretical results, we conclude that the O(3P) reaction is characterized by a minor adiabatic channel leading to OCCCN (cyanoketyl) + H (experimental BF = 0.10 ± 0.05), while the dominant channel (BF = 0.90 ± 0.05) occurs via intersystem crossing to the underlying singlet PES and leads to formation of 1HCCN (cyanomethylene) + CO. The O(1D) reaction is characterized by the same two channels, with the relative CO/H yield being slightly larger. Considering the recorded reactive signal and the calculated entrance barrier, we estimate that the rate coefficient for reaction O(3P) + HC3N at 300 K is in the 10-12 cm3 molec-1 s-1 range. Our results are expected to be useful to improve astrochemical and photochemical models. In addition, they are also relevant in combustion chemistry, because the thermal decomposition of pyrrolic and pyridinic structures present in fuel-bound nitrogen generates many nitrogen-bearing compounds, including cyanoacetylene.

Reaction N(2D) + CH2CCH2 (Allene): An Experimental and Theoretical Investigation and Implications for the Photochemical Models of Titan.

We report on a combined experimental and theoretical investigation of the N(2D) + CH2CCH2 (allene) reaction of relevance in the atmospheric chemistry of Titan. Experimentally, the reaction was investigated (i) under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy (E c) of 33 kJ/mol to determine the primary products and the reaction micromechanism and (ii) in a continuous supersonic flow reactor to determine the rate constant as a function of temperature from 50 to 296 K. Theoretically, electronic structure calculations of the doublet C3H4N potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction mechanism. The reaction is found to proceed via barrierless addition of N(2D) to one of the two equivalent carbon-carbon double bonds of CH2CCH2, followed by the formation of several cyclic and linear isomeric C3H4N intermediates that can undergo unimolecular decomposition to bimolecular products with elimination of H, CH3, HCN, HNC, and CN. The kinetic experiments confirm the barrierless nature of the reaction through the measurement of rate constants close to the gas-kinetic rate at all temperatures. Statistical estimates of product branching fractions (BFs) on the theoretical PES were carried out under the conditions of the CMB experiments at room temperature and at temperatures (94 and 175 K) relevant for Titan. Up to 14 competing product channels were statistically predicted with the main ones at E c = 33 kJ/mol being formation of cyclic-CH2C(N)CH + H (BF = 87.0%) followed by CHCCHNH + H (BF = 10.5%) and CH2CCNH + H (BF = 1.4%) the other 11 possible channels being negligible (BFs ranging from 0 to 0.5%). BFs under the other conditions are essentially unchanged. Experimental dynamical information could only be obtained on the overall H-displacement channel, while other possible channels could not be confirmed within the sensitivity of the method. This is also in line with theoretical predictions as the other possible channels are predicted to be negligible, including the HCN/HNC + C2H3 (vinyl) channels (overall BF < 1%). The dynamics and product distributions are dramatically different with respect to those observed in the isomeric reaction N(2D) + CH3CCH (propyne), where at a similar E c the main product channels are CH2NH (methanimine) + C2H (BF = 41%), c-C(N)CH + CH3 (BF = 32%), and CH2CHCN (vinyl cyanide) + H (BF = 12%). Rate coefficients (the recommended value is 1.7 (±0.2) × 10-10 cm3 s-1 over the 50-300 K range) and BFs have been used in a photochemical model of Titan's atmosphere to simulate the effect of the title reaction on the species abundance (including any new products formed) as a function of the altitude.

Intersystem crossing in the entrance channel of the reaction of O(3P) with pyridine.

Two quantum effects can enable reactions to take place at energies below the barrier separating reactants from products: tunnelling and intersystem crossing between coupled potential energy surfaces. Here we show that intersystem crossing in the region between the pre-reactive complex and the reaction barrier can control the rate of bimolecular reactions for weakly coupled potential energy surfaces, even in the absence of heavy atoms. For O(3P) plus pyridine, a reaction relevant to combustion, astrochemistry and biochemistry, crossed-beam experiments indicate that the dominant products are pyrrole and CO, obtained through a spin-forbidden ring-contraction mechanism. The experimental findings are interpreted-by high-level quantum-chemical calculations and statistical non-adiabatic computations of branching fractions-in terms of an efficient intersystem crossing occurring before the high entrance barrier for O-atom addition to the N-atom lone pair. At low to moderate temperatures, the computed reaction rates prove to be dominated by intersystem crossing.

The N(2D) + CH2CHCN (Vinyl Cyanide) Reaction: A Combined Crossed Molecular Beam and Theoretical Study and Implications for the Atmosphere of Titan.

The reaction of electronically excited nitrogen atoms, N(2D), with vinyl cyanide, CH2CHCN, has been investigated under single-collision conditions by the crossed molecular beam (CMB) scattering method with mass spectrometric detection and time-of-flight (TOF) analysis at the collision energy, Ec, of 31.4 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) have been performed to assist in the interpretation of the experimental results and characterize the overall reaction micromechanism. Statistical (Rice-Ramsperger-Kassel-Marcus, RRKM) calculations of product branching fractions (BFs) on the theoretical PES have been carried out at different values of temperature, including the one corresponding to the temperature (175 K) of Titan's stratosphere and at a total energy corresponding to the Ec of the CMB experiment. According to our theoretical calculations, the reaction is found to proceed via barrierless addition of N(2D) to the carbon-carbon double bond of CH2═CH-CN, followed by the formation of cyclic and linear intermediates that can undergo H, CN, and HCN elimination. In competition, the N(2D) addition to the CN group is also possible via a submerged barrier, leading ultimately to N2 + C3H3 formation, the most exothermic of all possible channels. Product angular and TOF distributions have been recorded for the H-displacement channels leading to the formation of a variety of possible C3H2N2 isomeric products. Experimentally, no evidence of CN, HCN, and N2 forming channels was observed. These findings were corroborated by the theory, which predicts a variety of competing product channels, following N(2D) addition to the double bond, with the main ones, at Ec = 31.4 kJ/mol, being six isomeric H forming channels: c-CH(N)CHCN + H (BF = 35.0%), c-CHNCHCN + H (BF = 28.1%), CH2NCCN + H (BF = 26.3%), c-CH2(N)CCN(cyano-azirine) + H (BF = 7.4%), trans-HNCCHCN + H (BF = 1.6%), and cis-HNCCHCN + H (BF = 1.3%), while C-C bond breaking channels leading to c-CH2(N)CH(2H-azirine) + CN and c-CH2(N)C + HCN are predicted to be negligible (0.02% and 0.2%, respectively). The highly exothermic N2 + CH2CCH (propargyl) channel is also predicted to be negligible because of the very high isomerization barrier from the initial addition intermediate to the precursor intermediate able to lead to products. The predicted product BFs are found to have, in general, a very weak energy dependence. The above cyclic and linear products containing an additional C-N bond could be potential precursors of more complex, N-rich organic molecules that contribute to the formation of the aerosols on Titan's upper atmosphere. Overall, the results are expected to have a significant impact on the gas-phase chemistry of Titan's atmosphere and should be properly included in the photochemical models.

The Reaction N(2D) + CH3CCH (Methylacetylene): A Combined Crossed Molecular Beams and Theoretical Investigation and Implications for the Atmosphere of Titan.

The reaction of excited nitrogen atoms N(2D) with CH3CCH (methylacetylene) was investigated under single-collision conditions by the crossed molecular beams (CMB) scattering method with mass spectrometric detection and time-of-flight analysis at the collision energy (Ec) of 31.0 kJ/mol. Synergistic electronic structure calculations of the doublet potential energy surface (PES) were performed to assist the interpretation of the experimental results and characterize the overall reaction micromechanism. Theoretically, the reaction is found to proceed via a barrierless addition of N(2D) to the carbon-carbon triple bond of CH3CCH and an insertion of N(2D) into the CH bond of the methyl group, followed by the formation of cyclic and linear intermediates that can undergo H, CH3, and C2H elimination or isomerize to other intermediates before unimolecularly decaying to a variety of products. Kinetic calculations for addition and insertion mechanisms and statistical (Rice-Ramsperger-Kassel-Marcus) computations of product branching fractions (BFs) on the theoretical PES were performed at different values of total energy, including the one corresponding to the temperature (175 K) of Titan's stratosphere and that of the CMB experiment. Up to 14 competing product channels were statistically predicted, with the main ones, at Ec = 31.0 kJ/mol, being the formation of CH2NH (methanimine) + C2H (ethylidyne) (BF = 0.41), c-C(N)CH + CH3 (BF = 0.32), CH2CHCN (acrylonitrile) + H (BF = 0.12), and c-CH2C(N)CH + H (BF = 0.04). Of the 14 possible channels, seven correspond to H displacement channels of different exothermicity, for a total H channel BF of ∼0.25 at Ec = 31.0 kJ/mol. Experimentally, dynamical information could only be obtained about the overall H channels. In particular, the experiment corroborates the formation of acrylonitrile + H, which is the most exothermic of all 14 reaction channels and is theoretically calculated to be the dominant H-forming channel (BF = 0.12). The products containing a novel C-N bond could be potential precursors to form other nitriles (C2N2, C3N) or more complex organic species containing N atoms in planetary atmospheres, such as those of Titan and Pluto. Overall, the results are expected to have a potentially significant impact on the understanding of the gas-phase chemistry of Titan's atmosphere and the modeling of that atmosphere.

Leading Interaction Components in the Structure and Reactivity of Noble Gases Compounds.

The nature, strength, range and role of the bonds in adducts of noble gas atoms with both neutral and ionic partners have been investigated by exploiting a fine-tuned integrated phenomenological-theoretical approach. The identification of the leading interaction components in the noble gases adducts and their modeling allows the encompassing of the transitions from pure noncovalent to covalent bound aggregates and to rationalize the anomalous behavior (deviations from noncovalent type interaction) pointed out in peculiar cases. Selected adducts affected by a weak chemical bond, as those promoting the formation of the intermolecular halogen bond, are also properly rationalized. The behavior of noble gas atoms excited in their long-life metastable states, showing a strongly enhanced reactivity, has been also enclosed in the present investigation.