Abstract It remains a long-standing challenge to predict the reaction kinetics of large complex hydrocarbon system from first principles. Exo-tricyclo[5.2.1.02,6]decane, which is further called tricyclodecane and which is the major component in JP-10 aviation fuel, and therefore its reaction with hydroxyl radical is very significant. We report high-level theoretical calculations of the rate constants of tricyclodecane + OH for the first time. We show that the exchange-correlation hybrid functional M06-2X with MG3S basis set provides an accurate and efficient calculation of the barrier heights and reaction energies. A total of 20 reaction pathways for hydrogen abstractions from chair and boat tricyclodecane conformations are considered for direct dynamics. Multi-structural canonical variational transition state theory with small-curvature tunneling (MS-CVT/SCT) is adopted to calculate the rate constants of the title reaction at 200–2000 K. The theoretical results obtained using MS-CVT/SCT with curvilinear coordinates are in fairly good agreement with the experimental measurements. We also determine the branching fractions as a function of temperature and find the tertiary abstraction from tricyclodecane is dominant. This work highlights the significance of modern DFT methods for studying combustion kinetics of large fuel molecules.

中文翻译：

---

大型复杂烃反应体系的直接动力学：OH 与外型三环癸烷（Jet Propelant-10 的主要成分）的反应

摘要 从第一性原理预测大型复杂烃体系的反应动力学仍然是一个长期存在的挑战。外型三环[5.2.1.02,6]癸烷，又称为三环癸烷，是JP-10航空燃料的主要成分，因此与羟基的反应非常显着。我们首次报告了三环癸烷 + OH 速率常数的高级理论计算。我们表明，具有 MG3S 基组的交换相关混合泛函 M06-2X 可以准确有效地计算势垒高度和反应能。从椅子和船三环癸烷构象中提取氢的总共 20 个反应途径被考虑用于直接动力学。采用小曲率隧穿多结构正则变分过渡态理论（MS-CVT/SCT）计算标题反应在200-2000 K下的速率常数。 使用曲线坐标MS-CVT/SCT获得的理论结果与实验测量值相当吻合。我们还确定了作为温度函数的支化分数，并发现三环癸烷的三级提取占主导地位。这项工作突出了现代 DFT 方法在研究大燃料分子燃烧动力学方面的重要性。我们还确定了作为温度函数的支化分数，并发现三环癸烷的三级提取占主导地位。这项工作突出了现代 DFT 方法在研究大燃料分子燃烧动力学方面的重要性。我们还确定了作为温度函数的支化分数，并发现三环癸烷的三级提取占主导地位。这项工作突出了现代 DFT 方法在研究大燃料分子燃烧动力学方面的重要性。