## 摘要

The thermal unimolecular decomposition of SiH_{4}
^{+} ion and its related reverse reactions, SiH_{3}
^{+} + H and SiH_{2}
^{+} + H_{2}, have been investigated by ab initio molecular orbital and quantum statistical variational RRKM theory calculations. The potential energy surface has been calculated at different levels of theory; the results at the highest level, CCSD(T)/CBS//CCSD(T)/6-311++G(3df,2p), show that the decomposition of SiH_{4}
^{+} can mainly occur via a barrierless channel giving SiH_{2}
^{+} + H_{2} lying 11.8 kcal/mol above the reactant, or via a transition state forming SiH_{3}
^{+}···H complex to be followed by a barrierless decomposition yielding SiH_{3}
^{+} + H lying 23.5 kcal/mol above the reactant. Barrierless processes were calculated using the CASPT2 and CASSCF methods with the 6-311++G(3df,2p) basis set and fitted with Morse potentials. The rate constants were predicted by solving master equations based on the RRKM theory at the E,J-resolved level; the results show that the channel SiH_{4}
^{+} → SiH_{2}
^{+} + H_{2} is predominate under PEVCD conditions. For H- and H_{2}-capturing by SiH_{3}
^{+} and SiH_{2}
^{+} ions, respectively, the rate constants were found to be weakly dependent on temperature at the high-pressure limit and decrease rapidly with pressure. The calculated heats of formation of the SiH_{x}
^{+} (x = 2–4) ions are in close agreement with available thermochemical data.

原文 | English |
---|---|

頁（從 - 到） | 1249-1264 |

頁數 | 16 |

期刊 | Plasma Chemistry and Plasma Processing |

卷 | 37 |

發行號 | 4 |

DOIs | |

出版狀態 | Published - 1 7月 2017 |

## 指紋

深入研究「Ab Initio Chemical Kinetics for the Thermal Decomposition of SiH_{4}

^{+}Ion and Related Reverse Ion–Molecule Reactions of Interest to PECVD of a-Si:H Films」主題。共同形成了獨特的指紋。