Electronic to vibrational and rotational energy transfer in S(1D)+CO quenching reaction: Ab initio MO and surface hopping trajectory studies

Abstract

Articles you may be interested inRo-vibrational quenching of CO (v = 1) by He impact in a broad range of temperatures: A benchmark study using mixed quantum/classical inelastic scattering theory J. Chem. Phys. 139, 074306 (2013); 10.1063/1.4818488Theoretical studies of the CO2-N2O van der Waals complex: Ab initio potential energy surface, intermolecular vibrations, and rotational transition frequencies J. Chem. Phys. 138, 044302 (2013); 10.1063/1.4776183The He + H 2 + → HeH+ + H reaction: Ab initio studies of the potential energy surface, benchmark timeindependent quantum dynamics in an extended energy range and comparison with experiments The collisional energy transfer reaction, S( 1 D)ϩCO→S( 3 P)ϩCO(v,J), has been studied by means of the ab initio MO ͑molecular orbital͒ and surface-hopping trajectory calculations. The potential-energy surfaces ͑PESs͒ calculated by the ab initio MO calculations showed that the singlet and triplet PESs ͓S( 1 D)ϩCO and S( 3 P)ϩCO͔ are composed of the attractive and repulsive potential curves, respectively. The strongly bond intermediate corresponding to SCO( 1 ͚) is found on the collision region on the singlet PES. The singlet and triplet PESs are crossed each other at region of around r(SϪC)ϭ2.4 Å with the seam of the conical intersection. By using the fitted ab initio PESs, three-dimensional surface-hopping trajectory calculations are performed under the Landau-Zener approximation. The calculated rotational and vibrational state distributions of the product CO(v,J) are composed of two components due to the contributions from both direct and complex channels. The calculations show that the quenching probability decreases gradually with increasing collision energy. This decrease is due to the fact that the branching ratio of direct to complex channels is varied as a function of collision energy. The mechanism of the energy transfer was discussed on the basis of the theoretical results.

A full dimensionalab initiodynamics study on the ionization processes of CF4

“…The classical trajectories have been produced on an analytically fitted potential energy surface (PES) as previously carried out by several groups [19] and also by us [21,22] †. However, it is not appropriate to predetermine the reaction surfaces of the present systems due to the large number of degrees of freedom (3N − 6 = 9, where N is the number of atoms in the system).…”

Mechanism of the product vibrational-rotational state selectivity in a gas phase ion-molecule collision

“…The dynamics calculations were performed in the same manner as described in our previous papers [10]. The potential energy surface, which was reported previously by us [9], is fitted to an analytical function by means of the least-squares method.…”

A Direct Ab Initio Dynamics Study on the Finite Temperature Effects on the Hyperfine Coupling Constant of a Weakly Bonded Complex

“…Direct Ab Initio Dynamics Calculation. In general, the classical trajectory is performed on an analytically fitted potential energy surface as previously carried out by us . However, it is not appropriate to predetermine the reaction surfaces of the present systems because of the large number of degrees of freedom (3N − 6 = 12 where N is number of atoms in the system).…”