Activation of dihydrogen by scandium ions

摘要

The interaction of3D,1D,3F, and1Dstates of Sc+with H2has been explored through the generation ofabinitiopotential energy surfaces for two different interaction geometries. We find that all components of the ground3Dand lowest1Dreact in an endothermic process to form ScH+(Dgr;H0=48.6 kcal/mol for the lowest product state from3DSc+) from a collinear interaction, and that four of the five components of each state are likely to proceed to this product fromanyinteraction geometry. The remaining component of1DSc+will form ScH+2in an activated process (Dgr;H0=minus;4.4 kcal/mol;Edeg;=12.8 kcal/mol). Inclusion of the effects of spinhyphen;orbit interactions reveals that the last3Dcomponent may also proceed adiabatically to ScH+2(Dgr;H0=+1.8 kcal/mol;Edeg;=19.0 kcal/mol) within a very narrow energy window. At least eight H2adduct states are also formed in the interaction with excited singlet and triplet Sc+states. We explore in detail the means by which Sc+activates the H2bond, and relate our results to other metalndash;H2systems.