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.

Unveiling the Reaction Mechanism of the N(2D) + Pyridine Reaction: Ring-Contraction versus 7-Membered-Ring Formation Channels.

Despite the relevance of the reactions of the prototypical nitrogen-containing six-membered aromatic molecule (N-heterocyclic) of pyridine (C6H5N) in environmental science, astrochemistry, planetary science, prebiotic chemistry, and materials science, few experimental/theoretical studies exist on the bimolecular reactions involving pyridine and neutral atomic/molecular radicals. We report a combined experimental and theoretical study on the elementary reaction of pyridine with excited nitrogen atoms, N(2D), aimed at providing information about the primary reaction products and their branching fractions (BFs). From previous crossed molecular beam (CMB) experiments with mass-spectrometric detection and present synergistic calculations of the reactive potential energy surface (PES) and product BFs we have unveiled the reaction mechanism. It is found that the reaction proceeds via N(2D) barrierless addition to pyridine that, via bridged intermediates followed by N atom "sliding" into the ring, leads to 7-membered-ring structures. They further evolve, mainly via ring-contraction mechanisms toward 5-membered-ring radical products and, to a smaller extent, via H-displacement mechanisms toward 7-membered-ring isomeric products and their isomers. Using the theoretical statistical estimates, an improved fit of the experimental data previously reported has been obtained, leading to the following results for the dominant product channels: C4H4N (pyrrolyl) + HCN (BF = 0.61 ± 0.20), C3H3N2 (1H-imidazolyl/1H-pyrazolyl) + C2H2 (BF = 0.11 ± 0.06), and C5H4N2 (7-membered-ring molecules or pyrrole carbonitriles) + H (BF = 0.28 ± 0.10). The ring-contraction product channels C4H4N (pyrrolyl) + HCN, C3H3N2 (1H-imidazolyl) + C2H2, C3H3N2 (1H-pyrazolyl) + C2H2, and C5H5 (cyclopentadienyl) + N2 have statistical BFs of 0.54, 0.09, 0.11, and 0.07, respectively. Among the H-displacement channels, the cyclic-CHCHCHCHNCN + H channel and cyclic-CHCHCHCHCN2 + H are theoretically predicted to have a comparable BF (0.07 and 0.06, respectively), while the other isomeric 7-membered-ring molecule + H channel has a BF of 0.03. Pyrrole-carbonitriles and 1H-ethynyl-1H-imidazole (+ H) isomeric channels have an overall BF of 0.03. Implications for the chemistry of Saturn's moon Titan and prebiotic chemistry, as well as for understanding the N-doping of graphene or carbon nanotubes, are noted.

An experimental and theoretical investigation of the N(2D) + C6H6 (benzene) reaction with implications for the photochemical models of Titan.

We report on a combined experimental and theoretical investigation of the N(2D) + C6H6 (benzene) reaction, which is of relevance in the aromatic chemistry of the atmosphere of Titan. Experimentally, the reaction was studied (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 (Ec) of 31.8 kJ mol-1 to determine the primary products, their branching fractions (BFs), and the reaction micromechanism, and (ii) in a continuous supersonic flow reactor to determine the rate constant as a function of temperature from 50 K to 296 K. Theoretically, electronic structure calculations of the doublet C6H6N 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 the aromatic ring of C6H6, followed by formation of several cyclic (five-, six-, and seven-membered ring) and linear isomeric C6H6N intermediates that can undergo unimolecular decomposition to bimolecular products. Statistical estimates of product BFs on the theoretical PES were carried out under the conditions of the CMB experiments and at the temperatures relevant for Titan's atmosphere. In all conditions the ring-contraction channel leading to C5H5 (cyclopentadienyl) + HCN is dominant, while minor contributions come from the channels leading to o-C6H5N (o-N-cycloheptatriene radical) + H, C4H4N (pyrrolyl) + C2H2 (acetylene), C5H5CN (cyano-cyclopentadiene) + H, and p-C6H5N + H. Rate constants (which are close to the gas kinetic limit at all temperatures, with the recommended value of 2.19 ± 0.30 × 10-10 cm3 s-1 over the 50-296 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 abundances as a function of the altitude.

Experimental and Theoretical Studies of Hyperthermal N + O2 Collisions.

The dynamics of hyperthermal N(4S) + O2 collisions were investigated both experimentally and theoretically. Crossed molecular beams experiments were performed at an average center-of-mass (c.m.) collision energy of ⟨Ecoll⟩ = 77.5 kcal mol-1, with velocity- and angle-resolved product detection by a rotatable mass spectrometer detector. Nonreactive (N + O2) and reactive (NO + O) product channels were identified. In the c.m. reference frame, the nonreactively scattered N atoms and reactively scattered NO molecules were both directed into the forward direction with respect to the initial direction of the reagent N atoms. On average, more than 90% of the available energy (⟨Eavl⟩ = 77.5 kcal mol-1) was retained in translation of the nonreactive products (N + O2), whereas a much smaller fraction of the available energy for the reactive pathway (⟨Eavl⟩ = 109.5 kcal mol-1) went into translation of the NO + O products, and the distribution of translational energies for this channel was broad, indicating extensive internal excitation in the nascent NO molecules. The experimentally derived c.m. translational energy and angular distributions of the reactive products suggested at least two dynamical pathways to the formation of NO + O. Quasiclassical trajectory (QCT) calculations were performed with a collision energy of Ecoll = 77 kcal mol-1 using two sets of potential energy surfaces, denoted as PES-I and PES-II, and these theoretical results were compared to each other and to the experimental results. PES-I is a reproducing kernel Hilbert space (RKHS) representation of multireference configurational interaction (MRCI) energies, while PES-II is a many-body permutation invariant polynomial (MB-PIP) fit of complete active space second order perturbation (CASPT2) points. The theoretical investigations were both consistent with the experimental suggestion of two dynamical pathways to produce NO + O, where reactive collisions may proceed on the doublet (12A') and quartet (14A') surfaces. When analyzed with this theoretical insight, the experimental c.m. translational energy and angular distributions were in reasonably good agreement with those predicted by the QCT calculations, although minor differences were observed which are discussed. Theoretical translational energy and angular distributions for the nonreactive N + O2 products matched the experimental translational energy and angular distributions almost quantitatively. Finally, relative yields for the nonreactive and reactive scattering channels were determined from the experiment and from both theoretical methods, and all results are in reasonable agreement.

Dynamics of Inelastic and Reactive Collisions of 16O(3P) with 15N18O.

The dynamics of O(3P) + NO collisions were investigated at a collision energy of ⟨Ecoll⟩ = 84.0 kcal mol-1 with the use of a crossed molecular beams apparatus employing a rotatable mass spectrometer detector. This experiment was performed with beams of 16O atoms and isotopically labeled 15N18O molecules to enable the products of reactive and inelastic scattering to be distinguished. Three scattering pathways were observed: inelastic scattering (16O + 15N18O), O-atom exchange (18O + 15N16O), and O-atom abstraction (18O16O + 15N). All product channels exhibited a preponderance of forward scattering, but scattering over a broad angular range was also observed for all products. For inelastic scattering, an average of 90% of the collision energy is retained in the translation of 16O and 15N18O. On the other hand, for O-atom exchange (which also leads to O + NO products), the collision energy is partitioned roughly evenly between the translation of 18O + 15N16O and the internal excitation of 15N16O. The available energy for O-atom abstraction is significantly lower than the collision energy because of the endoergicity of this reaction, but the available energy is again roughly evenly partitioned between the translation of 18O16O + 15N and the internal excitation of the molecular (O2) product. The relative yields of the three scattering pathways were determined to be 0.751 for inelastic scattering, 0.220 for O-atom exchange, and 0.029 for O-atom abstraction.

Substituent Effects on the Electronic Spectroscopy of Four-Carbon Criegee Intermediates.

Atmospheric ozonolysis of biogenic and anthropogenic alkenes generates zwitterionic carbonyl oxide intermediates (R1R2C═O+O-), known as Criegee intermediates, with different structural motifs and conformations. This study reports a systematic laboratory study of substituent effects on the electronic spectroscopy of four-carbon Criegee intermediates (CIs) with methyl-ethyl (MECI) and isopropyl (IPCI) groups, which are isomers produced in ozonolysis of asymmetric branched alkenes. The four-carbon CIs are separately generated by an alternative synthetic route, and spectroscopically characterized on the strong π* ← π transition associated with the carbonyl oxide group in a pulsed supersonic expansion with VUV photoionization at 118 nm and UV-induced depletion of the m/z 88 signal. The resultant broad and unstructured UV spectral features for MECI and IPCI are peaked at ca. 320 and 330 nm, respectively, with large absorption cross-sections of ca. 10-17 cm2. Comparisons are made with the four-carbon CIs formed in isoprene ozonolysis, methyl vinyl ketone oxide (MVK-oxide) and methacrolein oxide (MACR-oxide), which have the same backbone connectivity as MECI and IPCI but have extended conjugation across the vinyl and carbonyl groups. A remarkable 50 nm shift of the peak absorption to longer wavelength is observed for MVK-oxide and MACR-oxide compared to MECI and IPCI, respectively. Vertical excitation energies computed theoretically agree well with the experimental findings, confirming that the spectral shifts are caused by the extended π conjugation in the isoprene-derived Criegee intermediates.

Photodissociation Dynamics of CH2OO on Multiple Potential Energy Surfaces: Experiment and Theory.

UV excitation of the CH2OO Criegee intermediate across most of the broad span of the (B 1A')-(X 1A') spectrum results in prompt dissociation to two energetically accessible asymptotes: O (1D) + H2CO (X 1A1) and O (3P) + H2CO (a 3A''). Dissociation proceeds on multiple singlet potential energy surfaces that are coupled by two regions of conical intersection (CoIn). Velocity map imaging (VMI) studies reveal a bimodal total kinetic energy release (TKER) distribution for the O (1D) + H2CO (X 1A1) products with the major and minor components accounting for ca. 40% and ca. 20% on average of the available energy (Eavl), respectively. The unexpected low TKER component corresponds to highly internally excited H2CO (X 1A1) products accommodating ca. 80% of Eavl. Full dimensional trajectory calculations suggest that the bimodal TKER distribution of the O (1D) + H2CO (X 1A1) products originates from two different dynamical pathways: a primary pathway (69%) evolving through one CoIn region to products and a smaller component (20%) sampling both CoIn regions enroute to products. Those that access both CoIn regions likely give rise to the more highly internally excited H2CO (X 1A1) products. The remaining trajectories (11%) dissociate to O (3P) + H2CO (a 3A'') products after traversing through both CoIn regions. The complementary experimental and theoretical investigation provides insight on the photodissociation of CH2OO via multiple dissociation pathways through two regions of CoIn that control the branching and energy distributions of products.

Crossed-Beam and Theoretical Studies of the O(3P, 1D) + Benzene Reactions: Primary Products, Branching Fractions, and Role of Intersystem Crossing.

Reliable modeling of hydrocarbon oxidation relies critically on knowledge of the branching fractions (BFs) as a function of temperature (T) and pressure (p) for the products of the reaction of the hydrocarbon with atomic oxygen in its ground state, O(3P). During the past decade, we have performed in-depth investigations of the reactions of O(3P) with a variety of small unsaturated hydrocarbons using the crossed molecular beam (CMB) technique with universal mass spectrometric (MS) detection and time-of-flight (TOF) analysis, combined with synergistic theoretical calculations of the relevant potential energy surfaces (PESs) and statistical computations of product BFs, including intersystem crossing (ISC). This has allowed us to determine the primary products, their BFs, and extent of ISC to ultimately provide theoretical channel-specific rate constants as a function of T and p. In this work, we have extended this approach to the oxidation of one of the most important species involved in the combustion of aromatics: the benzene (C6H6) molecule. Despite extensive experimental and theoretical studies on the kinetics and dynamics of the O(3P) + C6H6 reaction, the relative importance of the C6H5O (phenoxy) + H open-shell products and of the spin-forbidden C5H6 (cyclopentadiene) + CO and phenol adduct closed-shell products are still open issues, which have hampered the development of reliable benzene combustion models. With the CMB technique, we have investigated the reaction dynamics of O(3P) + benzene at a collision energy (Ec) of 8.2 kcal/mol, focusing on the occurrence of the phenoxy + H and spin-forbidden C5H6 + CO and phenol channels in order to shed further light on the dynamics of this complex and important reaction, including the role of ISC. Concurrently, we have also investigated the reaction dynamics of O(1D) + benzene at the same Ec. Synergistic high-level electronic structure calculations of the underlying triplet/singlet PESs, including nonadiabatic couplings, have been performed to complement and assist the interpretation of the experimental results. Statistical (RRKM)/master equation (ME) computations of the product distribution and BFs on these PESs, with inclusion of ISC, have been performed and compared to experiment. In light of the reasonable agreement between the CMB experiment, literature kinetic experimental results, and theoretical predictions for the O(3P) + benzene reaction, the so-validated computational methodology has been used to predict (i) the BF between the C6H5O + H and C5H6 + CO channels as a function of collision energy and temperature (at 0.1 and 1 bar), showing that their increase progressively favors radical (phenoxy + H)-forming over molecule (C5H6 + CO and phenol stabilization)-forming channels, and (ii) channel-specific rate constants as a function of T and p, which are expected to be useful for improved combustion models.

Photodissociation dynamics of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis.

The electronic spectrum of methyl vinyl ketone oxide (MVK-oxide), a four-carbon Criegee intermediate derived from isoprene ozonolysis, is examined on its second π* ← π transition, involving primarily the vinyl group, at UV wavelengths (λ) below 300 nm. A broad and unstructured spectrum is obtained by a UV-induced ground state depletion method with photoionization detection on the parent mass (m/z 86). Electronic excitation of MVK-oxide results in dissociation to O (1D) products that are characterized using velocity map imaging. Electronic excitation of MVK-oxide on the first π* ← π transition associated primarily with the carbonyl oxide group at λ > 300 nm results in a prompt dissociation and yields broad total kinetic energy release (TKER) and anisotropic angular distributions for the O (1D) + methyl vinyl ketone products. By contrast, electronic excitation at λ ≤ 300 nm results in bimodal TKER and angular distributions, indicating two distinct dissociation pathways to O (1D) products. One pathway is analogous to that at λ > 300 nm, while the second pathway results in very low TKER and isotropic angular distributions indicative of internal conversion to the ground electronic state and statistical unimolecular dissociation.

Combined Experimental and Theoretical Studies of the O(3P) + 1-Butene Reaction Dynamics: Primary Products, Branching Fractions, and Role of Intersystem Crossing.

Information on the detailed mechanism and dynamics (primary products, branching fractions (BFs), and channel specific rate constants as a function of temperature) for many important combustion reactions of O(3P) with unsaturated hydrocarbons is still lacking. We report synergistic experimental/theoretical studies on the mechanism and dynamics of the O(3P) + 1-C4H8 (1-butene) reaction by combining crossed molecular beam (CMB) experiments with soft electron ionization mass-spectrometric detection and time-of-flight analysis at 10.5 kcal/mol collision energy (Ec) to high-level ab initio electronic structure calculations of the underlying triplet and singlet potential energy surfaces (PESs) and statistical Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) computations of BFs including intersystem crossing (ISC). The reactive interaction of O(3P) with 1-butene is found to mainly break apart the 4-carbon atom chain, leading to the radical product channels ethyl + vinoxy (BF = 0.34 ± 0.11), methyl + C3H5O (BF = 0.28 ± 0.09), formyl + propyl (BF = 0.17 ± 0.05), ethyl + acetyl (BF = 0.014 ± 0.007), and butanal radical (ethylvinoxy) + H (BF = 0.013 ± 0.004), and molecular product channels formaldehyde + propenylidene/propene (BF = 0.15 ± 0.05) and butenone (ethyl ketene) + H2 (BF = 0.037 ± 0.015). As some of these products can only be formed via ISC from triplet to singlet PESs, from BFs an extent of ISC of 50% is inferred. This value is significantly larger than that recently observed for O(3P) + propene (22%) at similar Ec, underlying the question of how important it is to consider nonadiabatic effects for these and similar combustion reactions. Comparison of the derived BFs with those of statistical (RRKM/ME) simulations on the ab initio coupled triplet/singlet PESs shows good agreement, warranting the use of the RRKM/ME approach to provide information on the variation of BFs with temperature and to derive channel specific rate constants as a function of temperature (T) and pressure (p). Notably, ISC is predicted to decrease strongly with increasing temperature (from about 70% at 300 K to 46% at Ec = 10.5 kcal/mol, and about 1% at 2000 K). The present results lead to a detailed understanding of the complex reaction mechanism of O(3P) + 1-butene and, by providing channel specific rate constants as a function of T and p, should facilitate the improvement of current fossil-fuel (1-butene) as well as biofuel (1-butanol) combustion models.

Crossed beam polyatomic reaction dynamics: recent advances and new insights.

Over the past ten years or so, great advances in our understanding of the dynamics of elementary (bimolecular) polyatomic reactions in the gas-phase have occurred. This has been made possible by critical improvements (a) in crossed molecular beam (CMB) instruments with rotating mass spectrometric detection and time-of-flight analysis, especially following the implementation of soft ionization (by tunable low energy electrons or vacuum-ultraviolet synchrotron radiation) for product detection with increased sensitivity and universal detection power, and (b) in REMPI-slice velocity map ion imaging (VMI) detection techniques in pulsed CMB experiments for obtaining product pair-correlated information through high-resolution measurements directly in the center of mass system. The improved universal CMB method is permitting us to identify all primary reaction products, characterize their formation dynamics, and determine the branching ratios (BRs) for multichannel non-adiabatic reactions, such as those of ground state oxygen atoms, O(3P), with unsaturated hydrocarbons (alkynes, alkenes, dienes). The improved slice VMI CMB technique is permitting us to explore at an unprecedented level of detail, through pair-correlated measurements, the reaction dynamics of a prototype polyatomic molecule such as CH4 (and isotopologues) in its ground state with a variety of important X radicals such as F, Cl, O, and OH. In this review, we highlight this recent progress in the field of CMB reaction dynamics, with an emphasis on the experimental side, but with the related theoretical work, at the level of state-of-the-art calculations of both the underlying potential energy surfaces and the reaction dynamics, noted throughout. In particular, the focus is (a) on the effect of molecular complexity and structure on product distributions, branching ratios and role of intersystem crossing for the multichannel, addition-elimination reactions of unsaturated hydrocarbons with O atoms, and (b) on the very detailed dynamics of the abstraction reactions of ground-state methane (and isotopologues) with atoms (F, Cl, O) and diatoms (OH), with inclusion of also rotational mode specificity in the vibrationally excited methane reactions.

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.

Theoretical Study of the Extent of Intersystem Crossing in the O(3P) + C6H6 Reaction with Experimental Validation.

The extent of intersystem crossing in the O(3P) + C6H6 reaction, a prototypical system for spin-forbidden reactions in oxygenated aromatic molecules, is theoretically evaluated for the first time. Calculations are performed using nonadiabatic transition-state theory coupled with stochastic master equation simulations and Landau-Zener theory. It is found that the dominant intersystem crossing pathways connect the T2 and S0 potential energy surfaces through at least two distinct minimum-energy crossing points. The calculated channel-specific rate constants and intersystem crossing branching fractions differ from previous literature estimates and provide valuable kinetic data for the investigation of benzene and polycyclic aromatic hydrocarbons oxidation in interstellar, atmospheric, and combustion conditions. The theoretical results are supported by crossed molecular beam experiments with electron ionization mass-spectrometric detection and time-of-flight analysis at 8.2 kcal/mol collision energy. This system is a suitable benchmark for theoretical and experimental studies of intersystem crossing in aromatic species.

Combined Experimental-Theoretical Study of the OH + CO → H + CO2 Reaction Dynamics.

A combined experimental-theoretical study is performed to advance our understanding of the dynamics of the prototypical tetra-atom, complex-forming reaction OH + CO → H + CO2, which is also of great practical relevance in combustion, Earth's atmosphere, and, potentially, Mars's atmosphere and interstellar chemistry. New crossed molecular beam experiments with mass spectrometric detection are analyzed together with the results from previous experiments and compared with quasi-classical trajectory (QCT) calculations on a new, full-dimensional potential energy surface (PES). Comparisons between experiment and theory are carried out both in the center-of-mass and laboratory frames. Good agreement is found between experiment and theory, both for product angular and translational energy distributions, leading to the conclusion that the new PES is the most accurate at present in elucidating the dynamics of this fundamental reaction. Yet, small deviations between experiment and theory remain and are presumably attributable to the QCT treatment of the scattering dynamics.