Institute for Solid State Theory and Center for Multiscale Theory and Computation, Westfälische Wilhelms-Universität Münster, Wilhelm-Klemm-Str. 10, 48149 Münster, Germany.
J Chem Phys. 2022 Dec 28;157(24):244101. doi: 10.1063/5.0129699.
ReaxFF reactive force fields have been parameterized for the ground and first excited states of azobenzene and its derivatives. In addition, an extended set of ab initio reference data ensures wide applicability, including to azosystems in complex environments. Based on the optimized force fields, nonadiabatic surface hopping simulations produce photoisomerization quantum yields and decay times of azobenzene, both in the gas phase and in n-hexane solution, in reasonable agreement with higher level theory and experiment. The transferability to other azo-compounds is illustrated for different arylazopyrazoles as well as ethylene-bridged azobenzene. Moreover, it has been shown that the model can be easily extended to adsorbates on metal surfaces. The simulation of the ring-opening of cyclobutene triggered by the photoisomerization of azobenzene in a macrocycle highlights the advantages of a reactive force field model.
ReaxFF 反应力场已针对偶氮苯及其衍生物的基态和第一激发态进行了参数化。此外，扩展的一组从头算参考数据确保了广泛的适用性，包括复杂环境中的偶氮系统。基于优化的力场，非绝热表面跳跃模拟产生了偶氮苯的光致异构化量子产率和衰减时间，无论是在气相还是在正己烷溶液中，都与更高水平的理论和实验结果相当吻合。通过对不同的芳基偶氮吡唑和乙烯桥联偶氮苯的研究，证明了该模型对其他偶氮化合物的可转移性。此外，还表明该模型可以很容易地扩展到金属表面上的吸附物。通过在大环中光致异构化偶氮苯来引发环丁烯的开环反应的模拟突出了反应力场模型的优势。
