Pressure dependence of butyl nitrate formation in the reaction of butylperoxy radicals with nitrogen oxide.

The yield of 1- and 2-butyl nitrates in the gas-phase reactions of NO with n-C4H9O2 and sec-C4H9O2, obtained from the reaction of F atoms with n-butane in the presence of O2, was determined over the pressure range of 100-600 Torr at 298 K using a high-pressure turbulent flow reactor coupled with a chemical ionization quadrupole mass spectrometer. The yield of butyl nitrates was found to increase linearly with pressure from about 3% at 100 Torr to about 8% at 600 Torr. The results obtained are compared with the available data concerning nitrate formation from NO reaction with other small alkylperoxy radicals. These results are also discussed through the topology of the lowest potential energy surface mainly obtained from DFT(B3LYP/aug-cc-pVDZ) calculations of the RO2 + NO reaction paths. The formation of alkyl nitrates, due essentially to collision processes, is analyzed through a model that points out the pertinent physical parameters of this system.

First-principles study of the interaction between NO and large carbonaceous clusters modeling the soot surface.

First-principles calculations are performed to characterize the NO adsorption on large carbonaceous clusters modeling the surface of soot. Adsorption on the face and on the edges of perfect and defective clusters is considered in the calculations. It is shown that the first situation corresponds to physisorption and requires taking into account long-range dispersion interactions in the calculations. In contrast, interaction of NO with the unsaturated edge of a defective cluster leads preferentially to a C-N rather than to a C-O chemical binding. This indicates that soot may be an efficient sink for NO in the troposphere only if it contains a high number of unsaturated carbon atoms. From a more fundamental point of view, this study also clearly evidences that quantum calculations have to be carefully conducted when considering the interaction between radical species and carbonaceous surfaces. Problems encountered with the choice of the functional used in density functional theory approaches as well as with the size of the basis set, spin multiplicity, and spin contamination have to be systematically addressed before any relevant conclusion can be drawn.

Surface temperature effects on the dynamics of N2 Eley-Rideal recombination on W(100).

Quasiclassical trajectories simulations are performed to study the influence of surface temperature on the dynamics of a N atom colliding a N-preadsorbed W(100) surface under normal incidence. A generalized Langevin surface oscillator scheme is used to allow energy transfer between the nitrogen atoms and the surface. The influence of the surface temperature on the N(2) formed molecules via Eley-Rideal recombination is analyzed at T = 300, 800, and 1500 K. Ro-vibrational distributions of the N(2) molecules are only slightly affected by the presence of the thermal bath whereas kinetic energy is rather strongly decreased when going from a static surface model to a moving surface one. In terms of reactivity, the moving surface model leads to an increase of atomic trapping cross section yielding to an increase of the so-called hot atoms population and a decrease of the direct Eley-Rideal cross section. The energy exchange between the surface and the nitrogen atoms is semi-quantitatively interpreted by a simple binary collision model.

Dynamical reaction pathways in Eley-Rideal recombination of nitrogen from W(100).

The scattering of atomic nitrogen over a N-pre-adsorbed W(100) surface is theoretically described in the case of normal incidence off a single adsorbate. Dynamical reaction mechanisms, in particular Eley-Rideal (ER) abstraction, are scrutinized in the 0.1-3.0 eV collision energy range and the influence of temperature on reactivity is considered between 300 and 1500 K. Dynamics simulations suggest that, though non-activated reaction pathways exist, the abstraction process exhibits a significant collision energy threshold (0.5 eV). Such a feature, which has not been reported so far in the literature, is the consequence of a repulsive interaction between the impinging and the pre-adsorbed nitrogens along with a strong attraction towards the tungsten atoms. Above threshold, the cross section for ER reaction is found one order of magnitude lower than the one for hot-atoms formation. The abstraction process involves the collision of the impinging atom with the surface prior to reaction but temperature effects, when modeled via a generalized Langevin oscillator model, do not affect significantly reactivity.

Dynamics simulation of N(2) scattering onto W(100,110) surfaces: A stringent test for the recently developed flexible periodic London-Eyring-Polanyi-Sato potential energy surface.

An efficient method to construct the six dimensional global potential energy surface (PES) for two atoms interacting with a periodic rigid surface, the flexible periodic London-Eyring-Polanyi-Sato model, has been proposed recently. The main advantages of this model, compared to state-of-the-art interpolated ab initio PESs developed in the past, reside in its global nature along with the small number of electronic structure calculations required for its construction. In this work, we investigate to which extent this global representation is able to reproduce the fine details of the scattering dynamics of N(2) onto W(100,110) surfaces reported in previous dynamics simulations based on locally interpolated PESs. The N(2)/W(100) and N(2)/W(110) systems are chosen as benchmarks as they exhibit very unusual and distinct dissociative adsorption dynamics although chemically similar. The reaction pathways as well as the role of dynamic trapping are scrutinized. Besides, elastic/inelastic scattering dynamics including internal state and angular distributions of reflected molecules are also investigated. The results are shown to be in fair agreement with previous theoretical predictions.

Transformation from angle-action variables to Cartesian coordinates for polyatomic reactions.

The transformation from angle-action variables to Cartesian coordinates is an important step of the semiclassical description of bimolecular collisions and photofragmentations. The basic reason is that dynamical conditions corresponding to molecular beam experiments are ideally generated in angle-action variables, whereas the classical equations of motion are ideally solved in Cartesian coordinates by standard numerical approaches. To our knowledge, this transformation is available in the literature only for atom-diatom arrangements. The goal of the present work is to derive it for diatom-polyatom ones. The analogous transformation for any type of arrangement may then be straightforwardly deduced from that presented here.

Exact, Born-Oppenheimer, and quantum-chemistry-like calculations in helium clusters doped with light molecules: The He2N2(X) system.

Helium clusters doped with diatomic molecules, He(N)-BC, have been recently studied by means of a quantum-chemistry-like approach. The model treats He atoms as "electrons" and dopants as "nuclei" in standard electronic structure calculations. Due to the large mass difference between He atoms and electrons, and to the replacement of Coulomb interactions by intermolecular potentials, it is worth assessing up to what extent are the approximations involved in this model, i.e., decoupling of the BC rotation from the He-atom orbital angular momenta and Born-Oppenheimer separation of the BC stretch versus the He motions, accurate enough. These issues have been previously tackled elsewhere for the (4)He(2)-Br(2)(X) system, which contains a heavy dopant [Roncero et al., Int. J. Quantum Chem. 107, 2756 (2007)]. Here, we consider a similar cluster but with a much lighter dopant such as N(2)(X). Although the model does not provide the correct energy levels for the cluster, positions and intensities of the main detectable lines of the vibrotational Raman spectrum at low temperature are accurately reproduced.

Mean potential phase space theory of chemical reactions.

A nonconventional application of phase space theory to the insertion reactions A+H(2), with A=C((1)D) and S((1)D), is presented. Instead of approximating the potential energies of interaction between separated fragments by their isotropic long-range contributions, as in the original theory, the latter are replaced by the accurate potential energies averaged with respect to Jacobi angles. The integral and differential cross sections obtained from this mean potential phase space theory (MPPST) turn out to be in very satisfying agreement with the benchmark predictions of the time-independent and time-dependent statistical quantum methods. The formal and numerical simplicity of MPPST with respect to any approach combining statistical assumptions and dynamical calculations makes it a promising tool for studying indirect polyatomic reactions.

On the theory of complex-forming chemical reactions: effect of parity conservation on the polarization of differential cross sections.

For complex-forming triatomic reactions such as the prototypical insertion reactions intensively studied in the last few years, quantum mechanical differential cross sections (DCS) present sharp forward/backward polarization peaks when the reagent rotational angular momentum quantum number j is zero. Moreover, the size of the peaks decreases rapidly with increasing j values so that for j = 3, they are no longer visible. In contrast, the polarization peaks are always missing in the classical mechanical DCSs. Apart from the peaks, however, the quantum and classical DCSs are usually in good agreement. In a recent rapid communication, we showed that the fundamental reason for the previous differences in the quantum and classical scenarios is that parity conservation leads in quantum mechanics to an angular momentum constraint without equivalent in classical mechanics. We also proposed a parity-restoring approximation leading to an accurate semi-classical description of the peaks. While only the main lines of the demonstration were given in the communication, we report here the whole developments. We also analyse why the peaks disappear when the reagent diatom is rotationally excited. As a by-product of the previous developments, we finally discuss the possibility of a general statistico-dynamical semiclassical approach.

Classical treatment of molecular collisions: striking improvement of the description of recoil energy distributions using Gaussian weighted trajectories.

The Gaussian weighting (GW) procedure, recently used in the classical treatment of molecular collisions, is a practical way of taking into account quantization of product vibrational actions. The goal of this brief communication is to show that the GW procedure may drastically improve the predictions of the recoil energy distribution between final fragments, an observable frequently measured in molecular beam experiments.

Parity conservation and polarization of differential cross sections in complex-forming chemical reactions.

For complex-forming chemical reactions, such as atom-diatom insertion reactions, quantum scattering and quantum statistical calculations usually predict sharp forward/backward peaks in the Differential Cross Sections (DCS). Conversely, the corresponding classical calculations are unable to reproduce these peaks. We show here that the basic reason for such an intriguing failure is that parity conservation is ignored in classical mechanics. A by-product of the analysis is a simple parity-restoring approximation that might significantly increase the ability of classical mechanics to describe DCSs over the whole angular range for the title processes.

Experimental and theoretical study of the reaction of OH radical with sabinene.

The gas phase sabinene + OH reaction is studied both experimentally and theoretically. Product yields from the reaction of sabinene with OH radicals have been measured in the absence of NOx in the UCC chamber (Cork, Ireland) and in the presence of NOx in the LISA chamber. Three primary carbonyl compounds were observed and quantified: acetone in [(24 +/- 6)%], formaldehyde in [(25 +/- 6)%] and sabinaketone in [(20 +/- 6)%]. The simultaneous quantification of these compounds is one of the major results of this work. The mechanism of product formation for this reaction has been studied using the quantum chemical DFT-B3LYP (6-31G(d,p) method. According to these calculations, the H-atom abstraction channel from sabinene by OH in the initial oxidation step may be taken into account to explain the acetone production. Sabinaketone and formaldehyde are mainly products of the addition channels of OH on the -C=CH2 double bond of sabinene. This is the first theoretical work on the title reaction.

Statisticodynamical approach of final state distributions in associative desorptions.

In associative desorptions governed by short-range forces, strong energy transfers between rotational, translational, and vibrational degrees of freedom of the nascent molecule take place beyond the transition state (TS). State or energy distributions are thus different at the TS and in the vacuum. Inspired by previous studies on unimolecular reactions, a statisticodynamical approach (SDA) is proposed which combines the transition state theory for the description of state distributions at the TS and a simple dynamical model to account for the effect of the post-TS dynamics on these distributions. The agreement found between the predictions of SDA, the much more demanding classical trajectory calculations, and experimental results in the case of H(2) and D(2) desorbing from Cu(111) is very satisfying. In addition to that, the formulation highlights some key factors of state distributions which would have been difficult to directly extract from a dynamical study. The notions of vibrational heating and rotational cooling are discussed within this context.

Molecular dynamics simulation study of water adsorption on hydroxylated graphite surfaces.

In this paper, we present results from molecular dynamic simulations devoted to the characterization of the interaction between water molecules and hydroxylated graphite surfaces considered as models for surfaces of soot emitted by aircraft. The hydroxylated graphite surfaces are modeled by anchoring several OH groups on an infinite graphite plane. The molecular dynamics simulations are based on a classical potential issued from quantum chemical calculations. They are performed at three temperatures (100, 200, and 250 K) to provide a view of the structure and dynamics of water clusters on the model soot surface. These simulations show that the water-OH sites interaction is quite weak compared to the water-water interaction. This leads to the clustering of the water molecules above the surface, and the corresponding water aggregate can only be trapped by the OH sites when the temperature is sufficiently low, or when the density of OH sites is sufficiently high.

Validity of phase space theory for atom-diatom insertion reactions.

Phase space theory (PST) is applied to the calculation of state-resolved integral and differential cross sections for the complex-forming atom-diatom insertion reactions A + H(2) --> AH(2) --> AH + H with A = C((1)D), S((1)D), O((1)D), and N((2)D). In the asymptotic channels, vibration motion is quantized while rotation and translation motions are treated classically. The approach is compared to exact quantum scattering calculations and quantum statistical models. Given the simplicity of PST, the agreement with the previous much more refined treatments is very satisfying. Although PST is a well-established theory, this work is, to our knowledge, the first such systematic comparison of its predictions with accurate quantum scattering and quantum statistical calculations.

Relaxation of hot atoms following H2 dissociation on a Pd111 surface.

We study the relaxation of hot H atoms produced by dissociation of H2 molecules on the Pd111 surface. Ab initio density-functional theory calculations and the "corrugation reducing procedure" are used to determine the interaction potential for a H atom in front of a rigid surface as well as its modification under surface-atom vibrations. A slab of 80 Pd atoms is used to model the surface together with "generalized Langevin oscillators" to account for energy dissipation to the bulk. We show that the energy relaxation is fast, about 75% of the available energy being lost by the hot atoms after 0.5 ps. As a consequence, the hot atoms do not travel more than a few angstroms along the surface before being trapped into the potential well located over the hollow site.