Journal of Physical Chemistry A, Vol.109, No.50, 11484-11494, 2005
Interactions in open-shell clusters: Ab initio study of pre-reactive complex O(P-3)+HCl
Van der Waals interactions between the ground-state triplet O(P-3) atom and the closed-shell HCl molecule are investigated in the pre-reactive region. Three adiabatic (two of A" symmetry and one of A' symmetry) and four non-relativistic diabatic potential energy surfaces are obtained by combining a restricted open-shell coupled cluster approach with the multireference configuration interaction method. The lower A" adiabatic potential surface has a single minimum (D-e = 589 cm(-1)) for a linear (OHCl)-H-... configuration. The upper A" potential has a weak (D-e = 65 cm(-1)) minimum for a linear (HClO)-O-... configuration. The A' adiabatic potential has a weak (124 cm(-1)) T-shaped minimum. Adiabatic potentials intersect once in the (OHCl)-H-... linear configuration and twice in the linear (HClO)-O-... geometry. The role of electrostatic interactions in shaping these potentials is discussed. The effects of spin-orbit coupling on this interaction are also investigated assuming a constant value of the SO parameter.