再探氯氟化物的热化学性质
Revisiting the thermochemistry of chlorine fluorides
AI总结：
本研究针对氯氟化物热化学计算问题，采用等键反应方案精确计算其标准生成焓，指出CCSD(T)原子化方案的精度局限，补充计算多温度热力学量并借助密度泛函理论研究消除曲线。
摘要：
本研究采用isodesmic反应（isodesmic reaction，等键反应）方案，对氯氟化物（ClF$_n$，n=1–7；Cl$_2$F和Cl$_3$F$_2$）的标准生成焓开展了精确计算。研究指出，对多数氯氟化物而言，若采用原子化方案，量子化学的金标准方法CCSD(T)无法预测出接近化学精度的焓值，这一结论得到了总原子化能结果的全面分析及这些化合物多参考特征考察的支撑。研究还计算了不同温度下的其他热力学量。为完善能量描述，本研究通过密度泛函理论研究了消除曲线，该方法是高关联波函数方法的一种计算成本可承受的替代方案。
英文摘要：
In this work, accurate calculations of standard enthalpies of formation of chlorine fluorides (ClF$_n$, n=1--7; Cl$_2$F and Cl$_3$F$_2$) were performed through the isodesmic reactions scheme. It is argued that, for many chlorine fluorides, the gold standard method of quantum chemistry (CCSD(T)) is not capable to predict enthalpy values nearing chemical accuracy if atomization scheme is used. This is underpinned by a thorough analysis of total atomization energy results and the inspection of multireference features of these compounds. Other thermodynamic quantities were also calculated at different temperatures. In order to complement the energetic description, elimination curves were studied through density functional theory as a computationally affordable alternative to highly correlated wave function-based methods.
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