Crossed molecular beam experiments and theoretical simulations on the multichannel reaction of toluene with atomic oxygen.

Despite extensive experimental and theoretical studies on the kinetics of the O(3P) + C7H8 (toluene) reaction and a pioneering crossed molecular beam (CMB) investigation, the branching fractions (BFs) of the CH3C6H4O(methylphenoxy) + H, C6H5O(phenoxy) + CH3, and spin-forbidden C5H5CH3 (methylcyclopentadiene) + CO product channels remain an open question, which has hampered the proper inclusion of this important reaction in the chemical modelling of various chemical environments. We report a CMB study with universal soft electron-ionization mass-spectrometric detection of the reactions O(3P,1D) + toluene at the collision energy of 34.7 kJ mol-1. From CMB data we have inferred the reaction dynamics and quantified the BFs of the primary products and the role of intersystem crossing (ISC). The CH3-elimination channel dominates (BF = 0.69 ± 0.22) in the O(3P) reaction, while the H-displacement and CO-formation channels are minor (BF = 0.22 ± 0.07 and 0.09 ± 0.05, respectively), with ISC accounting for more than 50% of the reactive flux. Synergistic transition-state theory (TST)-based master equation simulations including nonadiabatic TST on ab initio coupled triplet/singlet potential energy surfaces were employed to compute the product BFs and assist in the interpretation of the CMB results. In the light of the good agreement between the theoretical predictions for the O(3P) + toluene reaction and the CMB results as well as the absolute rate constant as a function of temperature (T) (from literature), the so-validated computational methodology was used to predict channel-specific rate constants as a function of T at 1 atm.

Photodissociation dynamics of methylamine in the blue edge of the A-band. II. The NH2 + CH3 channel.

The photodissociation dynamics leading to the C-N bond cleavage in methylamine (CH3NH2) are investigated upon photoexcitation in the blue edge of the first absorption A-band, in the 198-204 nm range. Velocity map images of the generated methyl (CH3) fragment detected in specific vibrational modes, i.e., ν = 0, ν1 = 1, and ν2 = 1, through resonance enhanced multiphoton ionization, are presented along with the corresponding translational energy distributions and the angular analysis. The experimental results are complemented by high-level ab initio calculations of potential energy curves as a function of the C-N bond distance. While a similar single Boltzmann-type contribution is observed in all the translational energy distributions measured, the speed-dependent anisotropy parameter obtained through the angular analysis reveals the presence of two different mechanisms. Prompt dissociation through the conical intersection between the Ã1A' first excited state and the ground state located in the exit channel is, indeed, revealed as a minor channel. In contrast, slow dissociation on the ground state, presumably from frustrated N-H bond cleavage trajectories, constitutes the major reaction pathway leading to the methyl formation.

Photodissociation dynamics of methylamine in the blue edge of the A-band. I. The H-atom elimination channel.

The photodissociation dynamics of methylamine (CH3NH2) upon excitation in the blue edge of the first absorption A-band, in the 198-203 nm range, are investigated by means of nanosecond pump-probe laser pulses and velocity map imaging combined with H(2S)-atom detection through resonance enhanced multiphoton ionization. The images and corresponding translational energy distributions for the H-atoms produced show three different contributions associated with three reaction pathways. The experimental results are complemented by high-level ab initio calculations. The potential energy curves computed as a function of the N-H and C-H bond distances allow us to draw a picture of the different mechanisms. Major dissociation occurs through N-H bond cleavage and it is triggered by an initial geometrical change, i.e., from a pyramidal configuration of the C-NH2 with respect to the N atom to a planar geometry. The molecule is then driven into a conical intersection (CI) seam where three outcomes can take place: first, threshold dissociation into the second dissociation limit, associated with the formation of CH3NH(Ã), is observed; second, direct dissociation after passage through the CI leading to the formation of ground state products; and third, internal conversion into the ground state well in advance to dissociation. While the two last pathways were previously reported at a variety of wavelengths in the 203-240 nm range, the former had not been observed before to the best of our knowledge. The role of the CI and the presence of an exit barrier in the excited state, which modify the dynamics leading the two last mechanisms, are discussed considering the different excitation energies used.

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.

Imaging the Photodissociation Dynamics and Fragment Alignment of CH2BrI at 193 nm.

The photodissociation dynamics and photofragment alignment of bromoiodomethane (CH2BrI) have been studied at 193 nm using a double experimental and theoretical approach. In addition, the ultraviolet (UV)-vacuum ultraviolet (VUV) absorption spectrum of gas phase CH2BrI has been measured in the photon energy range of 5-11 eV using the VUV Fourier transform spectrometer (FTS) at the VUV beamline DESIRS of the synchrotron SOLEIL facility. The slice imaging technique in combination with resonance enhanced multiphoton ionization (REMPI) detection of the Br(2PJ) and I(2PJ) (with J = 3/2 and 1/2 for Br/I and Br*/I*, respectively) atomic photofragments have been used to produce experimental translational energy and angular distributions, which were analyzed to deliver, on one hand, the partitioning of the available energy among the different degrees-of-freedom of the photofragments and, on the other, the photofragment polarization in terms of aqk(p) alignment parameters. The experimental measurements were rationalized in terms of high-level ab initio calculations of vertical excitation energies, transition dipole moments and potential energy curves (PECs) along different reaction coordinates to provide a complete picture of the photodissociation dynamics. The results indicate that for excitation at 193 nm, prompt C-X cleavage (with X being either halogen atom, Br or I) competes with fast internal conversion and consequent stochastic dissociation in lower electronic states. In the case of the CH2Br + I(2P3/2)/I*(2P1/2) channels, the dynamics are greatly biased toward the stochastic dissociation process due to both the particular PECs landscape and the unfavored excitation of the CH2BrI ensemble with respect to the C-I molecular axis at this excitation energy. The ab initio PECs provide a tentative path for the fast dissociation process in either case. For the C-Br bond breakage, excitation to the 13A' electronic state and predissociation through the 11A'/11A″ or 12A'/12A″ states, leading to direct dissociation through the 10A'/9A″ states, appear as the most consistent dynamics. For the C-I channel, predissociation does not become a reliable possibility and a fast internal conversion may precede dissociation through the repulsive 6A'/6A″ and 4A'/4A″ states. The large content of rotational and vibrational excitation of the polyatomic cofragments is justified through the soft impulsive model and the geometrical changes produced along the dissociation pathway. Strikingly, the aqk(p) alignment parameters obtained for the Br(2P3/2) and I(2P3/2) photoproducts indicate that the rotational angular momentum of the CH2X (X = I or Br) cofragment appears highly constrained along the recoil direction. Finally, this work presents a highly plausible explanation for the branching ratio of secondary dissociation processes in the photodynamics of CH2BrI at 193 nm.

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.

Dynamics of the photodissociation of ethyl iodide from the origin of the B band. A slice imaging study.

The photodissociation dynamics and stereodynamics of ethyl iodide from the origin of the second absorption B-band have been investigated combining pulsed slicFe imaging with resonance enhanced multiphoton ionization (REMPI) detection of all fragments, I(2P3/2), I*(2P1/2) and C2H5. The I*(2P1/2) atom action spectrum recorded as a function of the excitation wavelength permits one to identify and select the 0 origin of this band at 201.19 nm (49 704 cm-1). Translational energy distributions and angular distributions for all fragments and semiclassical Dixon's bipolar moments for the C2H5 fragment are presented and discussed along with high-level ab initio calculations of potential energy curves as a function of the C-I distance. A predissociative mechanism governs the dynamics where in a first step a bound Rydberg state corresponding to the 5pπI→ 6sI transition is populated by the 201.19 nm-photon absorption. A curve crossing with a repulsive state located within the Franck-Condon geometry leads to direct dissociation into the major channel C2H5 + I*(2P1/2). A small amount of I(2P3/2) atoms is nevertheless observed and presumably attributed to a second curve crossing with a repulsive state from the A-band.