A detailed combustion mechanism of hydrocarbon fuels usually contains a large number of reactions and need to have kinetic data assigned to them, where the rate constants are usually given by approximate estimation leading to inaccuracies. In this work, a method for construction transition state (TS) and an isodesmic reactions correction scheme for accurate and automatic calculation of rate constants have been designed. These methods are tested using the cyclization reactions of QOOH radicals and the concerted elimination reactions of RO₂ radicals. The results show that the automatic TS construction method is effective to construct the initial guesses of the transition states, the isodesmic reactions corrected results are close to the CCSD(T) results and some of the rate constants are significantly different from the rate constants used in the automated mechanism generator, indicating that it is necessary and significant to perform on-the-fly accurate calculation of rate constants in an automated mechanism generator.

碳氢化合物燃料的详细燃烧机理通常包含大量反应，并且需要为其分配动力学数据，其中速率常数通常由近似估计得出，从而导致误差。在这项工作中，已经设计了一种用于精确自动计算速率常数的构造过渡态（TS）方法和等渗反应校正方案。使用QOOH自由基的环化反应和RO ₂的协同消除反应对这些方法进行了测试部首。结果表明，自动TS构造方法可以有效地构造过渡态的初始猜测，等渗反应校正的结果接近CCSD（T）结果，并且某些速率常数与所用的速率常数显着不同。自动机制生成器，这表明在自动机制生成器中进行实时准确的速率常数计算是必要且重要的。