Theoretical studies of the stereodynamics for the reaction H + LiH ⁺(v = 0, j = 0) → Li⁺+ H₂

Abstract

Theoretical studies of the stereodynamics for the chemical reaction H + LiH⁺(v = 0, j = 0) → Li⁺+ H₂ were conducted using the quasi-classical trajectory (QCT) method on the three-dimensional potential energy surface [J. Chem. Phys. 119, 11241 (2003)] at three collision energies (0.01, 0.05 and 0.1 eV). The calculated DCS results indicate that the products tend to both extreme forward and backward scattering. Because the potential well lying in the product valley is a weak van der Waals well, the forward–backward scattering is asymmetric. The calculated P(θ_r ) shows that the rotational angular momentum polarization of the product molecule is quite strong and insensitive to increasing collision energy. For the title reaction, it is not a deep well but a shallow Van der Waals well about 0.286 eV below the Li⁺+ H₂ asymptote on the PES. Hence, the reaction mainly behaves as an exoergic reaction rather than an insertion mechanism. The distributions of indicate that j′ is not only aligned, but also oriented preferentially along the positive direction of the y-axis. The distributions indicate that the product molecules are preferentially polarized perpendicular to the scattering plane and that the reaction is dominated by an in-plane mechanism.

Keywords:

• ab initio
• electronic structure
• quantum chemistry
• computational chemistry

Acknowledgements

The authors are very grateful to Dr Ilaria Pino for providing the accurate three-dimensional PES code. This work was supported by the National Natural Science Foundation of China (grant Nos. 10604012 and 10974023) and SRF for ROCS, SEM (2006).