Electronic structure calculations and transition state theory are used to compute rate coefficients for the low-temperature oxidation of diethyl ether. Additional rate coefficients are computed to account for rovibrationally excited species that react with O₂ prior to thermalization in a process known as non-Boltzmann reactions. A detailed, low-temperature kinetic mechanism for DEE combustion is developed. Ignition delay curves are computed using two mechanisms, one that includes only thermal reactions and a second that also includes 8 non-Boltzmann reactions. Simulations suggest that at an initial pressure of 1 atm and temperatures below 800 K, the inclusion of non-Boltzmann reactions decreases the predicted ignition delay by a factor of 2 or more. As the pressure increases, the effective contribution of these reactions diminishes. These results suggest that non-Boltzmann phenomena can have a significant effect on real-world applications.

电子结构计算和过渡态理论用于计算乙醚低温氧化的速率系数。计算额外的速率系数以说明与O ₂反应的边缘激发物质在被称为非玻尔兹曼反应的过程中加热之前。开发了一种用于DEE燃烧的详细的低温动力学机理。使用两种机制来计算点火延迟曲线，一种机制仅包含热反应，另一种机制还包含8种非玻尔兹曼反应。模拟表明，在1个大气压的初始压力和低于800 K的温度下，非玻尔兹曼反应的加入将预测的点火延迟降低了2倍或更多倍。随着压力增加，这些反应的有效作用减小。这些结果表明，非玻尔兹曼现象可能会对实际应用产生重大影响。