Fu Christopher D, He Yi, Pfaendtner Jim
Department of Chemical Engineering , University of Washington , Seattle , Washington 98195 , United States.
College of Chemical and Biological Engineering , Zhejiang University , Hangzhou 310027 , P. R. China.
J Phys Chem A. 2019 Apr 11;123(14):3080-3089. doi: 10.1021/acs.jpca.8b11780. Epub 2019 Mar 28.
In this study we utilize biased, reactive molecular dynamics (ReaxFF MD) simulations to quantitatively assess the impact of external electric fields on the kinetics of toluene oxidation and pyrolysis. We observe that the application of a strong external electric field significantly accelerates the kinetics of toluene oxidation, while having no effect on the pyrolysis reactions. When viewed through the lens of harmonic transition state theory, this phenomenon can be ascribed to the increase in the change of entropy between the transition state and reactants for the oxidation reactions. This conclusion is further verified with a model that relates the change in entropy as a function of field strength to predict the kinetics of toluene oxidation, which accounts for the total variance in the data recovered from simulation.
在本研究中，我们利用有偏的反应分子动力学（ReaxFF MD）模拟来定量评估外部电场对甲苯氧化和热解动力学的影响。我们观察到，施加强外部电场会显著加速甲苯氧化的动力学，而对热解反应没有影响。从谐波过渡态理论的角度来看，这种现象可归因于氧化反应中过渡态与反应物之间熵变的增加。通过一个将熵变作为场强函数的模型来预测甲苯氧化的动力学，进一步验证了这一结论，该模型解释了模拟中回收数据的总方差。
