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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dissociation of 1,1,1-Trifluoroethane Is an Intrinsic RRKM Process: Classical Trajectories and Successful Master Equation Modeling
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Dissociation of 1,1,1-Trifluoroethane Is an Intrinsic RRKM Process: Classical Trajectories and Successful Master Equation Modeling

机译：1,1,1-三氟乙烷的解离是内在的RRKM过程：经典轨迹和成功的主方程建模

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摘要

Rate constants for thermal decomposition of 1,1,1-trifluoroethane (CH3CF3) in the high-temperature falloff region were previously reported to have an unusual pressure dependence that could not be explained by Rice-Ramsperger-Kassel-Marcus (RRKM) theory in combination with unimolecular master equation analysis. This study investigates the dynamics of the CH3CF3 dissociation and the energy transfer of CH3CF3 in collisions with Ar and Kr by classical trajectory calculations on a global potential energy surface constructed from a large number of quantum chemical calculations. The simulations showed that the ensemble-averaged CH3CF3 populations decay with single exponential profiles that have rate constants close to those predicted by RRKM theory, indicating that the microcanonical ensemble is maintained during decomposition. The trajectory calculation also indicated that a significant portion of the HF product is formed in its vibrationally excited state. Such observation motivated this study to correct some of the reported rate constants for the CH3CF3 decomposition. With the correction applied, the experimental rate constants were well reproduced by the RRKM/master equation calculation using the collisional energy transfer parameters that were also obtained from trajectory calculations. Overall, the title reaction is demonstrated to be another successful example of RRKM/master equation modeling.
机译：先前曾报道过在高温衰减区域中1,1,1-三氟乙烷（CH3CF3）的热分解速率常数具有不寻常的压力依赖性，Rice-Ramsperger-Kassel-Marcus（RRKM）理论无法解释该常数。结合单分子主方程分析。这项研究调查了CH3CF3的解离动力学和与Ar和Kr碰撞时CH3CF3的能量转移，方法是通过大量量子化学计算构建的全球势能面上的经典轨迹计算。仿真表明，合计平均的CH3CF3种群以单一指数分布衰减，该分布的速率常数接近于RRKM理论预测的速率常数，表明在分解过程中维持了微正则合奏。轨迹计算还表明，HF产品的很大一部分是在其振动激发状态下形成的。这种观察促使这项研究纠正了CH3CF3分解的某些报道的速率常数。进行校正后，使用碰撞能量转移参数（也从轨迹计算获得）通过RRKM /主方程计算很好地重现了实验速率常数。总体而言，标题反应被证明是RRKM /主方程建模的另一个成功示例。

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