| Abstract
| - A study of both the singlet and triplet potential energy surfacesof the [H3, P2]+ system hasbeen carried outusing the G2 procedure. Various stable structures along with anumber of reaction mechanisms for the reactionof both the 1D and 3P electronic states ofP+ with phosphine have been elucidated. The moststable isomeron the singlet potential energy surface, which corresponds to thespecies resulting from a hydrogen migrationin the P+−PH3 complex, lies 127.3 kcal/molbelow the reactants level, P+(1D) +PH3(1A1). On thetripletsurface, on the other hand, the P+−PH3ion−molecule complex is the most stable isomer, 84.4kcal/molbelow P+(3P) +PH3(1A1). Variousreaction paths for both the molecular and atomic hydrogeneliminationhave been fully characterized. For both spin multiplicities theH2 abstraction is found to be favored withrespect to H abstraction, in full agreement with available experimentaldata. Finally, we have also discussedthe hydrogen and/or charge-transfer reaction between singlet1D and triplet 3P states of P+with phosphine.
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