Abstract Stable species and saddle points on the C5H11O potential energy surface relevant for 1-pentanol pyrolysis and combustion have been determined starting from the terminal adduct of the OH + 1-pentene reaction. A large number of stationary points were explored automatically with the KinBot software at the M06-2X/6-311++G(d,p) level. The kinetically relevant stationary points have been further characterized using UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) quantum chemistry calculations. The entrance channel consists of a barrierless outer transition state leading into a van der Waals well followed by a submerged saddle point, overall described with an effective two-transition-state model. The master equation has been solved to obtain pressure- and temperature-dependent rate coefficients for all reactions on the potential energy surface in the 300–2500 K temperature range and 0.01–100 atm pressure range. The newly obtained rate coefficients have been implemented in a kinetic model for the thermal decomposition of 1-pentanol diluted in a nitrogen stream. We measured the conversion of major species using gas chromatography with a flame ionization detector, and two-dimensional gas chromatography with time-of-flight mass spectrometric and flame ionization detectors in the effluent of a flow reactor at 0.17 MPa between 913 and 1023 K. Comparison of the simulated versus the experimental data acquired in this work shows that the reactions found by KinBot, for which earlier only poor estimates existed, are of significant importance to correctly describe conversion and product selectivities. It proves to be possible to generate adequate chemical models automatically provided that the underlying high-level ab initio data is computationally affordable.

中文翻译：

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1-戊醇自由基的分解和异构化及1-戊醇的热解

摘要 从 OH + 1-戊烯反应的末端加合物开始，确定了与 1-戊醇热解和燃烧相关的 C5H11O 势能面上的稳定物种和鞍点。使用 KinBot 软件在 M06-2X/6-311++G(d,p) 级别自动探索了大量静止点。使用 UCCSD(T)-F12a/cc-pVTZ-F12//M06-2X/6-311++G(d,p) 量子化学计算进一步表征了动力学相关的驻点。入口通道由一个无障碍的外部过渡态组成，通向范德瓦尔斯井，然后是一个淹没的鞍点，总体上用有效的双过渡态模型进行描述。已求解主方程以获得 300-2500 K 温度范围和 0.01-100 atm 压力范围内势能表面上所有反应的压力和温度相关速率系数。新获得的速率系数已在用于在氮气流中稀释的 1-戊醇热分解的动力学模型中实施。我们使用带有火焰离子化检测器的气相色谱法和带有飞行时间质谱和火焰离子化检测器的二维气相色谱法测量了流动反应器流出物中的主要物质的转化率，压力为 0.17 MPa，温度介于 913 和 1023 K 之间。在这项工作中获得的模拟数据与实验数据的比较表明，KinBot 发现的反应，早期只存在较差的估计，对正确描述转化率和产品选择性非常重要。事实证明，只要底层的高级 ab initio 数据在计算上是负担得起的，就可以自动生成足够的化学模型。