G2 study of triplet [H 4 , Si, P] + potential energy surface: Mechanism for reaction of P + ( 3 P) with silane

A G2 search of the triplet [H 4 , Si, P] + potential energy surface (PES) 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 hydrogen atoms from the silicon to the phosphorus atom, lies 67.3 kcal/mol below the reactants' level. The P + (SINGLE BOND)SiH 4 ion‐molecule complex also has remarkable stability, 20.4 kcal/mol. Bond properties were calculated and are discussed for all the stable species found on the PES. Various exothermic reaction paths were also fully characterized. The abstractions of a hydrogen molecule and a hydrogen atom, yielding species with P(SINGLE BOND)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. © 1997 by John Wiley & Sons, Inc.