Global 1 1A" potential energy surface of CH2 and quantum dynamics of a sideways insertion mechanism for the C(1D) + H2 --> CH(2pi) + H reaction.
A global adiabatic potential energy surface (PES) corresponding to the second singlet state 1 1A" (1 1B1) of CH2 has been computed in a similar way as the first singlet state 1 1A' in our previous work [B. Bussery-Honvault et al., J. Chem. Phys., 2001, 115, 10 701]. This PES has a calculated well depth of 79.9 kcal mol(-1) relative to the C(1D) + H2 asymptote and correlates to CH(2pi) + H. It presents large barriers in the C(1D) + H2 arrangement for both collinear and perpendicular geometries but no barrier for geometries about 60 degrees and leads to a sideways insertion mechanism for the reaction C(1D) + H2 --> CH(2pi) + H. The ab initio calculations were carried out for 4644 geometries and the resulting energies were fitted to a many-body expansion. Accurate three-dimensional quantum mechanical scattering calculations have been performed for the C(1D) + H2(v = 0, j = 0) reaction on this ab initio 1 1A" PES in the collision energy range [0-11.5 kcal mol(-1)]. The J = 0 reaction probabilities show dense resonance structures as those obtained with the 1 1A' PES. However some different dynamical features have been found.
Bussery-Honvault
Béatrice
B
PALMS, UMR 6627 du CNRS and Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France. Beatrice.Honvault@univ-rennes1.fr
Julien
Jérôme
J
Honvault
Pascal
P
Launay
Jean-Michel
JM