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A theoretical study of the F(2P) + OH(2Pi) --> HF(1Sigma+) + O(3P) reactive collisions is carried out on a new global potential energy surface (PES) of the ground 3A" adiabatic electronic state. The ab initio calculations are based on multireference configuration interaction calculations, using the aug-cc-pVTZ extended basis sets of Dunning et al. A functional representation of the PES shows no nominal barrier to reaction, contrary to previous results by others. Wave packet and quasiclassical trajectory calculations have been performed for this PES to study the F + OH(v = 0,j) reactive collision. The comparison was performed at fixed and constant values of the total angular momentum from 0 to 110 and relative translational energy up to 0.8 eV. The reaction presents a dynamical barrier, essentially due to the zero-point energy for the bending vibration near the saddle point. This determines two different reaction mechanisms. At energies higher than approximately 0.125 eV the reaction is direct, while below that value it is indirect and mediated by heavy-light-heavy resonances. Such resonances, also found in the simulations of the photodetachment spectrum of the triatomic anion, manifest themselves in the quasiclassical simulations, too, where they are associated to periodic orbits.

Global three-dimensional adiabatic potential-energy surfaces for the excited 2(3)A" and 1(3)A' triplet states of OHF are obtained to study the F(2P)+OH(2pi)-->O(3P)+HF(1sigma+) reaction. Highly accurate ab initio calculations are obtained for the two excited electronic states and fitted to analytical functions with small deviations. The reaction dynamics is studied using a wave-packet treatment within a centrifugal sudden approach, which is justified by the linear transition state of the two electronic states studied. The reaction efficiency presents a marked preference for perpendicular orientation of the initial relative velocity vector and the angular momentum of the OH reagent, consistent in the body-fixed frame used with an initial collinear geometry which facilitates the access to the transition state. It is also found that the reaction cross section presents a rather high threshold so that, in an adiabatic picture, the two excited triplet states do not contribute to the rate constant at room temperature. Thus, only the lowest triplet state leads to reaction under these conditions and the simulated rate constants are too low as compared with the experimental ones. Such disagreement is likely to be due to nonadiabatic transitions occurring at the conical intersections near the transition state for this reaction.

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The dynamics of the deuteron-proton exchange D(+) + H(2) → HD + H(+) reaction on its ground 1(1)A' potential energy surface has been the subject of a theoretical study for collision energies below 1.5 eV. The results obtained with three theoretical approaches: quasi-classical trajectory (QCT), statistical quasi-classical trajectory (SQCT), and accurate time-independent quantum mechanical (QM) calculations are compared in the range of collision energies from 5 meV to 0.2 eV. The QM calculations included all total angular momentum quantum numbers, J, up to J(max) ≈ 40 and all the Coriolis couplings. For higher collision energies, the comparison was restricted to the QCT and SQCT results given the enormous computational cost implied in the QM calculations. Reaction cross sections as a function of collision energy (excitation functions) for various initial rovibrational states have been determined and compared with the corresponding results for the endothermic H(+) + D(2) → HD + D(+) isotopic variant. The excitation function for the title reaction decays monotonically with collision energy as expected for an exothermic reaction without a barrier, in contrast to the behaviour observed in the mentioned H(+) + D(2) (v = 0, j ≤ 3). Reaction probabilities as a function of J (opacity functions) at several collision energies calculated with the different approaches were also examined and important differences between them were found. The effect of using the gaussian binning procedure that preserves, to a large extent, the zero point energy, as compared to the standard histogram binning in the QCT calculations, is also examined. At low collision energy, the best agreement with the accurate QM results is given by the SQCT data, although they tend to overestimate the reactivity. The deviations from the statistical behaviour of the QCT data at higher energies are remarkable. Nevertheless, on the whole, the title reaction can be deemed more statistical than the H(+) + D(2) reaction.

Articles you may be interested inKinetic and dynamic studies of the Cl(2 P u) + H2O( X ̃ 1 A 1) → HCl( X ̃ 1Σ+) + OH( X ̃ 2Π) reaction on an ab initio based full-dimensional global potential energy surface of the ground electronic state of ClH2O J. Chem. Phys. 139, 074302 (2013); 10.1063/1.4817967State-to-state dynamics of H+HD→H 2 +D at 0.5 eV: A combined theoretical and experimental study Rotational and translational energy distributions of CN (v=0,J) from the hot atom reactions: H+XCN→HX+CN (v=0,J), where X=Br , Cl, and CN An analytical representation of the ground potential energy surface ( 2 A ′ ) of the H+Cl 2 →HCl+Cl and Cl+HCl→HCl+Cl reactions, based on ab initio calculations A detailed and comprehensive study of the dynamics has been performed using quasiclassical trajectory calculations on a recent version of the ground 1 1 AЈ potential energy surface ͑PES͒ ͓M. T. Martínez et al., Phys. Chem. Chem. Phys. 2, 589 ͑2000͔͒ for this system. This PES was shown to account very well for the various experimental results available for the HOCl system. It has been found that this reaction occurs following different mechanisms depending on whether the HClO, HOCl, or both wells are visited in the course of the reaction. The different scalar and vector properties are strongly dependent on the type of mechanism through which a reaction takes place. Calculations have also been carried out to determine the distribution of collision times for each of the different mechanisms, and the time evolution of the differential cross section. For both reaction chemical channels the backward scattering is delayed with respect to the appearance of forward scattering. Although this reaction has been considered traditionally as an insertion reaction, it has been found that the first stages of the close interaction between the three atoms correspond to an attachment type of mechanism.

The effect of reactant polarisation on the dynamics of the title reaction at collision energies up to 1.6 eV is analysed in depth. The analysis takes advantage of two novel theoretical concepts: intrinsic reaction properties and stereodynamical portraits. Exact quantum methods are used to determine the polarisation moments that quantify the intrinsic reactant polarisation at various levels of detail, including or not product state and/or scattering angle resolution. The data is then examined with the aid of stereodynamical portraits, which facilitate the rationalisation of the stereochemical effects that are relevant for the reaction dynamics. This allows for detailed characterisations of the so-called direct and delayed reaction mechanisms.

ion-molecule reactions is compared with the results of quantum mechanical (QM), quasiclassical trajectory (QCT), and statistical quasiclassical trajectory (SQCT) calculations. The dynamical observables considered include specific rate coefficients as a function of the translational energy, E T , thermal rate coefficients in the 100-500 K temperature range. In addition, kinetic energy spectra (KES) of the D + ions reactively scattered in H + + D 2 collisions are also presented for translational energies between 0.4 eV and 2.0 eV. For the two reactions, the best global agreement between experiment and theory over the whole energy range corresponds to the QCT calculations using a Gaussian binning (GB) procedure, which gives more weight to trajectories whose product vibrational action is closer to the actual integer QM values. The QM calculations also perform well, although somewhat worse over the more limited range of translational energies where they are available (E T o 0.6 eV and E T o 0.2 eV for the H + + D 2 and D + + H 2 reactions, respectively). The worst agreement is obtained with the SQCT method, which is only adequate for low translational energies. The comparison between theory and experiment also suggests that the most reliable rate coefficient measurements are those obtained with the merged beams technique. It is worth noting that none of the theoretical approaches can account satisfactorily for the experimental specific rate coefficients of H + + D 2 for E T r 0.2 eV although there is a considerable scatter in the existing measurements. On the whole, the best agreement with the experimental laboratory KES is obtained with the simulations carried out using the state resolved differential cross sections (DCSs) calculated with the QCT-GB method, which seems to account for most of the observed features. In contrast, the simulations with the SQCT data predict kinetic energy spectra (KES) considerably cooler than those experimentally determined.