Institution: | a National Institute of Materials and Chemical Research, 1-1, Higashi, Tsukuba, Ibaraki 305-0046, Japan b Institute for Molecular Science, Okazaki, Aichi, 444-8585, Japan |
Abstract: | The isomerization reaction from c-OSiH2O to t-OSiHOH, a vital reaction to understand the spontaneous ignition of silane, has been reinvestigated with Gaussian-2 theory and the CASSCF(6,6) method. It has been found that the reaction proceeds through two consecutive steps; i.e., c-OSiH2O undergoes isomerization to yield w-OSiH2O, and then the latter is converted to t-OSiHOH. The G-2 energy of the transition state of the latter process is 4.3 kcal/mol higher than that of the former. However, the G-2 energy of this higher transition state plus H atom is still 4.8 kcal/mol lower than that of the original reactants of SiH3 + O2. |