G2 study of triplet [H4, Si, P]+ potential energy surface: Mechanism for reaction of P+ (3P) with silane

✍ Scribed by Cruz, Elso M.; Lopez, Xabier; Sarobe, Mart�n; Coss�o, Fernando P.; Ugalde, Jesus M.

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 314 KB
• Volume: 18
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/(sici)1096-987x(19970115)18:1<9::aid-jcc2>3.0.co;2-u

✦ Synopsis

A G2 search of the triplet H , Si, P potential energy surface PES was carried 4 out, along with a study of a number of mechanisms for the reaction of the P q Ž 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 kcalrmol below the reactants' level. The P q ᎏSiH 4 ion᎐molecule complex also has remarkable stability, 20.4 kcalrmol. 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 PᎏSi bonds, have comparable kinetic hindrance, although release of molecular hydrogen was found to be more exothermic. Finally, hydrogen andror charge q Ž 3 . transfer reactions between P P and silane are also discussed.