G2 STUDY OF TRIPLET [H-4,SI,P](-ENERGY SURFACE - MECHANISM FOR REACTION OF P+(P-3) WITH SILANE() POTENTIAL)

A G2 search of the triplet [H-4, Si, P](+) potential energy surface (P ES) was carried out, along with a study of a number of mechanisms for the reaction of the P+ ((3)p) ion with silane. The most stable isomer, which corresponds to the species resulting from transferring three hy drogen atoms from the silicon to the phosphorus atom, lies 67.3 kcal/m ol below the reactants' level. The P+-SiH4 ion-molecule complex also h as remarkable stability, 20.4 kcal/mol. Bond properties were calculate d and are discussed for all the stable species found on the PES. Vario us exothermic reaction paths were also fully characterized. The abstra ctions of a hydrogen molecule and a hydrogen atom, yielding species wi th P-Si bonds, have comparable kinetic hindrance, although release of molecular hydrogen was found to be more exothermic. Finally, hydrogen and/or charge transfer reactions between P+ ((3)p) and silane are also discussed. (C) 1997 by John Wiley & Sons, Inc.