Abstract Chemical dynamics simulations are performed to study the unimolecular dissociation of C6H6–C6Cl6 (Bz-HCB) complex at a temperature range of 1000–2000 K. The intramolecular and intermolecular potential energy parameters are optimized to reproduce the experimental frequencies, equilibrium energy and the minimum energy geometry of the complex. The microcanonical and canonical rate constants are fit to the harmonic classical Rice–Ramsperger–Kassel–Marcus (RRKM) and transition state theory (TST) equations, respectively. The role of anharmonicity on the dissociation of the complex is examined by considering the modified TST equation with the inclusion of an exponential anharmonic correction. The requirement of such a correction in analyzing the dissociation dynamics of Bz-HCB complex is validated by a Monte Carlo based calculation.

中文翻译：

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C6H6-C6Cl6配合物的单分子解离动力学和非谐性的影响

摘要 进行化学动力学模拟以研究 C6H6–C6Cl6 (Bz-HCB) 复合物在 1000–2000 K 温度范围内的单分子解离。优化分子内和分子间势能参数以重现实验频率、平衡能量和复合体的最小能量几何。微正则和正则速率常数分别拟合谐波经典 Rice-Ramsperger-Kassel-Marcus (RRKM) 和过渡态理论 (TST) 方程。通过考虑包含指数非谐波校正的修改后的 TST 方程来检查非谐性对复合体解离的作用。在分析 Bz-HCB 复合物的解离动力学时进行这种校正的要求通过基于蒙特卡罗的计算得到验证。