Quasi-classical trajectory study of the H + CO2 → HO + CO reaction on a new ab initio based potential energy surface

Abstract

A detailed quasi-classical trajectory study of the H + CO(2) → HO + CO reaction is reported on an accurate potential energy surface based on ab initio data. The influence of the vibrational and rotational excitations of CO(2) was investigated up to the collision energy of 2.35 eV. It was found that the total reaction integral cross section increases monotonically with the collision energy, consistent with experimental results. The excitation of the CO(2) bending vibration enhances the reaction, while the excitation in its asymmetric stretching vibration inhibits the reaction. The calculated thermal rate constants are in excellent agreement with experiment. At the state-to-state level, the rotational state distributions of the HO product are in good agreement with experimental results, while those for the CO product are much hotter than measurements. The calculated differential cross sections are dominated by forward scattering, suggesting that the lifetime of the HOCO intermediate may not be sufficiently long to render the reaction completely statistical.

Influence of denticity and combined soft–hard strategy on the interaction of picolinic-type ligands with NpO2+

“…38) basis set (BS1), which was used for geometry optimization and frequency calculations, and another one with the larger basis set 6-311++G(d,p) (BS2) to rene energies. [39][40][41] In both basis sets, the Np atom was treated by a small-core quasi-relativistic effective core potentials (5f-in-valence RECPs) for the 60 core electrons, and the corresponding valence basis set adopted a contraction scheme of (14s13p10d8f6g)/[10s9p5d4f3g] (ECP60MWB basis) [42][43][44] to describe the valence shells.…”

State‐to‐state reaction dynamics for the reactions of atom N with radicals

“…The IMLS, PIP, NN, and PIP‐NN fitting methods are based on the solution of a weighted least‐squares problem with rigorous implementations of different basis functions, which can be extended to high dimensional PESs easily. The PIP‐NN method was developed very recently by combination of the PIP and NN methods, which leads to a smaller root mean square error and is efficient for fitting the PESs of molecular systems, especially for polyatomic systems . In this review, the PESs of the N + OH, N + CH, and N + C 2 reaction systems are all fitted with the cubic spline interpolation method, which is simple and direct.…”

Theoretical/experimental comparison of deep tunneling decay of quasi-bound H(D)OCO to H(D) + CO2

“…Several global representations of the PES have been developed. [17][18][19][20][21][22][23][24] Two of these PES have been explicitly used in comparison to the PPC measurements. The LTSH PES 19 was unfavorably contrasted 16 to an adjustable potential optimized to reproduce measured tunneling of H(D)OCO to H + CO 2 .…”