Kinetic and Mechanistic Study of the Reactions of NO Radicals with Unsaturated Aldehydes: 2-Butenal, 2-Methyl-2-butenal, and 3-Methyl-2-butenal.

The kinetics and mechanisms of the gas-phase reactions of NO radical with two branched unsaturated aldehydes, 2-methyl-2-butenal (also called 2-methyl-crotonaldehyde) and 3-methyl-2-butenal (or 3-methyl-crotonaldehyde), have been investigated by experimental and theoretical approaches. Kinetic data were also provided, for comparison, for 2-butenal (or crotonaldehyde). Experiments were performed in a simulation chamber at 295 ± 3 K and atmospheric pressure.

Kinetic Study of the Gas-Phase Reactions of Nitrate Radicals with Methoxyphenol Compounds: Experimental and Theoretical Approaches.

The gas-phase reactions of five methoxyphenols (three disubstituted and two trisubstituted) with nitrate radicals were studied in an 8000 L atmospheric simulation chamber at atmospheric pressure and 294 ± 2 K. The NO3 rate constants were investigated with the relative kinetic method using PTR-ToF-MS and GC-FID to measure the concentrations of the organic compounds. The rate constants (in units of cm(3) molecule(-1) s(-1)) determined were: 2-methoxyphenol (guaiacol; 2-MP), k(2-MP) = (2.

Reversible addition of the OH radical to p-cymene in the gas phase: multiple adduct formation. Part 2.

A flash photolysis-resonance fluorescence (FP-RF) system was used to study the p-cymene (PC) + OH reaction at temperatures between 299 and 349 K in helium. Triexponential functions were fitted to groups of observed OH decay curves according to a model considering a reversible addition to form two adducts as thermolabile reservoirs of OH. Compared to Part 1 of this paper, consideration of a second adduct strongly improved the fits to our measurements, and the rate constants for the major pathways were optimized between 299 and 349 K.

Theoretical study of the gas-phase reactions of NO3 radical with a series of trans-2-unsaturated aldehydes: from acrolein to trans-2-octenal.

The density functional theory with the BH&HLYP functional has been used in this work to clarify discrepancies found in the literature about the effect of the increasing carbon chain on the reactivity of trans-2-alkenals from acrolein (C3) to trans-2-octenal (C8) with nitrate radical. In this work, it was found that (i) the alkyl chain length of the unsaturated aldehydes has little or no influence on the NO3 reaction rate coefficients (ii) the abstraction of the aldehydic hydrogen from the alkenal is always dominant (83% for trans-2-butanal to trans-2-octenal). The addition channel, which mainly concerns the β addition, has a small influence (17% of the total reaction for the whole series).

Gas-phase reaction of hydroxyl radical with hexamethylbenzene.

Aromatic hydrocarbons are important components of polluted ambient air. The reaction of OH radicals with hexamethylbenzene (HMB) is a prototype system to study ipso addition leading eventually to dealkylation. We have investigated the OH + HMB and OD + HMB reactions between 323 and 433 K using a discharge fast-flow reactor coupled to a time-of-flight mass spectrometer with single-photon VUV photoionization (10.

Water adsorption on oxidized single atomic vacancies present at the surface of small carbonaceous nanoparticles modeling soot.

Quantum calculations are used to study the interaction of water molecules with carbonaceous clusters containing one single carbon atom vacancy. This is a simple but realistic way to model the active surfaces found in soot emitted by aircrafts. Prior to water adsorption, the atomic vacancy is oxidised by an approaching oxygen molecule, which is also likely to occur behind planes.

Quasi-classical statistico-dynamical description of polyatomic photo-dissociations: state-resolved distributions.

An alternative methodology to investigate indirect polyatomic processes with quasi-classical trajectories is proposed, which effectively avoids any binning or weighting procedure while provides rovibrational resolution. Initial classical states are started in terms of angle-action variables to closely match the quantum experimental conditions and later transformed into Cartesian coordinates, following an algorithm very recently published [J. Chem.

Water vapor effect on the HNO3 yield in the HO2 + NO reaction: experimental and theoretical evidence.

The influence of water vapor on the production of nitric acid in the gas-phase HO(2) + NO reaction was determined at 298 K and 200 Torr using a high-pressure turbulent flow reactor coupled with a chemical ionization mass spectrometer. The yield of HNO(3) was found to increase linearly with the increase of water concentration reaching an enhancement factor of about 8 at [H(2)O] = 4 x 10(17) molecules cm(-3) ( approximately 50% relative humidity). A rate constant value k(1bw) = 6 x 10(-13) cm(3) molecule(-1) s(-1) was derived for the reaction involving the HO(2)xH(2)O complex: HO(2)xH(2)O + NO --> HNO(3) (1bw), assuming that the water enhancement is due to this reaction.

Adsorption of water molecules on partially oxidized graphite surfaces: a molecular dynamics study of the competition between OH and COOH sites.

In this paper, molecular dynamic simulations are used to study the adsorption of water molecules on partially oxidized graphite surfaces containing COOH and OH sites. More specially, the competition between the OH and COOH sites with respect to water adsorption is characterized at three different temperatures (200, 250 and 300 K). The simulations show a strong preferential clustering of the water molecules around the COOH sites irrespective of the temperature.

Study of the H+O2 reaction by means of quantum mechanical and statistical approaches: the dynamics on two different potential energy surfaces.

The possible existence of a complex-forming pathway for the H+O(2) reaction has been investigated by means of both quantum mechanical and statistical techniques. Reaction probabilities, integral cross sections, and differential cross sections have been obtained with a statistical quantum method and the mean potential phase space theory. The statistical predictions are compared to exact results calculated by means of time dependent wave packet methods and a previously reported time independent exact quantum mechanical approach using the double many-body expansion (DMBE IV) potential energy surface (PES) [Pastrana et al.

A comparative study of the Si+O(2)-->SiO+O reaction dynamics from quasiclassical trajectory and statistical based methods.

The dynamics of the singlet channel of the Si+O(2)-->SiO+O reaction is investigated by means of quasiclassical trajectory (QCT) calculations and two statistical based methods, the statistical quantum method (SQM) and a semiclassical version of phase space theory (PST). The dynamics calculations have been performed on the ground (1)A(') potential energy surface of Dayou and Spielfiedel [J. Chem.

Cross sections and rate constants for the C(3P)+OH(X 2Pi)-->CO(X 1Sigma+)+H(2S) reaction using a quasiclassical trajectory method.

First quasiclassical trajectory calculations have been carried out for the C(3P)+OH(X 2Pi)-->CO(X 1Sigma+)+H(2S) reaction using a recent ab initio potential energy surface for the ground electronic state, X 2A', of HCO/COH. Total and state-specific integral cross sections have been determined for a wide range of collision energies (0.001-1 eV).

Time dependent wave packet and statistical calculations on the H + O(2) reaction.

The H + O(2)--> OH + O reaction has been theoretically investigated by means of an exact time dependent wave packet method and two statistical approaches: a recently developed statistical quantum model and phase-space theory. The exhaustive analysis of reaction probabilities at a zero total angular momentum would, in principle, reveal the existence of a complex-forming mechanism at low collision energies (E(c) = 1.15 eV), whereas deviations from a statistical behaviour at higher energies may be interpreted as the onset of a direct abstraction pathway which favours the production of highly excited rotational states of the OH fragment in its ground vibrational state.

A reinvestigation of the kinetics and the mechanism of the CH3C(O)O2 + HO2 reaction using both experimental and theoretical approaches.

The kinetics and the mechanism of the reaction CH(3)C(O)O(2)+ HO(2) were reinvestigated at room temperature using two complementary approaches: one experimental, using flash photolysis/UV absorption technique and one theoretical, with quantum chemistry calculations performed using the density functional theory (DFT) method with the three-parameter hybrid functional B3LYP associated with the 6-31G(d,p) basis set. According to a recent paper reported by Hasson et al., [J.

Dynamical study of H2 and D2 desorbing from a Cu(111) surface.

A theoretical study of H(2) and D(2) desorbing from Cu(111) is reported. The study makes use of the LEPS PES of Dai and Zhang [J. Chem.

On the statisticodynamical approach of final state distributions in simple bond fissions.

When the energy available to the products of a barrierless unimolecular reaction is of the order of 100 cm(-1), phase space theory leads usually to a good description of product state distributions. This is no longer the case for energies of the order of 1000 cm(-1). It seems, for example, that the excitation of the recoil energy distribution is underestimated by the theory as suggested by experimental results on the photodissociations of C(2)O and NCO.

Statisticodynamical approach of state distributions in the products of four-atom planar unimolecular reactions. II. Validation and distribution shape analysis in the barrier case.

In the first part of this series, we proposed a statisticodynamical approach of state distributions in the products of four-atom planar unimolecular reactions governed by short-range forces. In this second part, the approach is tested against quasiclassical trajectory calculations on an ab initio potential energy surface. The process considered is the fragmentation of isocyanic acid in the first excited singlet electronic state.

Statisticodynamical approach of state distributions in the products of four-atom planar unimolecular reactions. I. Formal developments for conserved vibrations.

Traditional statistical approaches, entirely based on transition state theory (TST), do not allow the description of rotational state distributions in the products of indirect reactions governed by short-range forces. Owing to the interpretative power of TST, this limitation has long been acting as a brake upon a deep understanding of determining attributes of indirect reaction dynamics. Recently, however, we developed a statisticodynamical approach (SDA) of final state distributions for triatomic unimolecular reactions [P.