A real wave packet based time-dependent method and a statistical quantum method have been used to study the He + NeH(+) (v, j) reaction with the reactant in various ro-vibrational states, on a recently calculated ab initio ground state potential energy surface. Both the wave packet and statistical quantum calculations were carried out within the centrifugal sudden approximation as well as using the exact Hamiltonian. Quantum reaction probabilities exhibit dense oscillatory pattern for smaller total angular momentum values, which is a signature of resonances in a complex forming mechanism for the title reaction. Significant differences, found between exact and approximate quantum reaction cross sections, highlight the importance of inclusion of Coriolis coupling in the calculations. Statistical results are in fairly good agreement with the exact quantum results, for ground ro-vibrational states of the reactant. Vibrational excitation greatly enhances the reaction cross sections, whereas rotational excitation has relatively small effect on the reaction. The nature of the reaction cross section curves is dependent on the initial vibrational state of the reactant and is typical of a late barrier type potential energy profile.
Real wave packet, statistical quantum, and quasiclassical trajectory methods were employed to study the dynamics of Ne + HeH+(v 0,j 0) → He + NeH+ reaction on an ab initio potential energy surface [J. Phys. Chem. A 2013, 117, 13070–13078]. Quantum and statistical quantum calculations were performed within the centrifugal sudden (CS) approximation as well as including the Coriolis coupling (CC). Dense oscillatory structures of the quantum reaction probabilities and fair agreement between quantum and statistical cross sections suggest a complex forming mechanism for the reaction. No significant differences between cross sections obtained within the CS and CC approaches are observed. Quasiclassical trajectory results give an excellent average description of the quantum CC results. At low collision energies, there is a substantial decrease in reactivity for the reaction upon rovibrational excitation. Initial state selected rate constants for the title reaction are calculated between 20 and 1000 K, and the calculated value at 300 K agrees quite well with the available experimental result. Reaction cross sections and rate constants are also compared with those calculated via the Langevin capture model for exothermic reactions.
The dynamics of the Ne + HeH(+)(v = 0, j = 0) → NeH(+)(v', j') + He reaction was analyzed in detail at the state-to-state level. A time-independent quantum mechanical (TIQM) method was applied to calculate rovibrational distributions and differential cross sections (DCSs), in comparison with quasi-classical trajectory and statistical quantum predictions. Possible changes in the dynamical mechanisms that define the process were also investigated as a function of the collision energy. At the lowest energy regime, the TIQM results produce a noticeably different cross section in comparison with previously reported time-dependent wave packet results. Although the statistical methods reproduce some dynamical features, especially as the energy increases, the marked preference for the forward scattering direction on the DCSs suggests that the reaction mainly follows a direct mechanism.
Initial state selected dynamics of the Ne + NeH(+)(v0 = 0, j0 = 0) → NeH(+) + Ne reaction is investigated by quantum and statistical quantum mechanical (SQM) methods on the ground electronic state. The three-body ab initio energies on a set of suitably chosen grid points have been computed at CCSD(T)/aug-cc-PVQZ level and analytically fitted. The fitting of the diatomic potentials, computed at the same level of theory, is performed by spline interpolation. A collinear [NeHNe](+) structure lying 0.72 eV below the Ne + NeH(+) asymptote is found to be the most stable geometry for this system. Energies of low lying vibrational states have been computed for this stable complex. Reaction probabilities obtained from quantum calculations exhibit dense oscillatory structures, particularly in the low energy region and these get partially washed out in the integral cross section results. SQM predictions are devoid of oscillatory structures and remain close to 0.5 after the rise at the threshold thus giving a crude average description of the quantum probabilities. Statistical cross sections and rate constants are nevertheless in sufficiently good agreement with the quantum results to suggest an important role of a complex-forming dynamics for the title reaction.
The study of the dynamics of atom–diatom reactions involving two rare gas (Rg) atoms and protons is of crucial importance given the astrophysical relevance of these processes. In a series of previous studies, we have been investigating a number of such Rg(1)+ Rg(2)H+→ Rg(2)+ Rg(1)H+ reactions by means of different numerical approaches. These investigations comprised the construction of accurate potential energy surfaces by means of ab initio calculations. In this work, we review the state-of-art of the study of these protonated Rg systems making special emphasis on the most relevant features regarding the dynamical mechanisms which govern these reactive collisions. The aim of this work therefore is to provide an as complete as possible description of the existing information regarding these processes.
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