Departamento de Química Física, Facultad de Química, Universidad de Vigo, Vigo, E-36310, Spain.
J Comput Chem. 2013 Sep 5;34(23):2020-31. doi: 10.1002/jcc.23357. Epub 2013 Jun 26.
We have performed high-level electronic structure computations on the most important species of the CH(n)P systems n = 1-3 to characterize them and provide reliable information about the equilibrium and vibrationally averaged molecular structures, rotational constants, vibrational frequencies (harmonic and anharmonic), formation enthalpies, and vertical excitation energies. Those chemical systems are intermediates for several important reactions and also prototypical phosphorus-carbon compounds; however, they are often elusive to experimental detection. The present results significantly complement their knowledge and can be used as an assessment of the experimental information when available. The explicitly correlated coupled-cluster RCCSD(T)-F12 method has been used for geometry optimizations and vibrational frequency calculations. Vibrational configuration interaction theory has been used to account for anharmonicity effects. Basis-set limit extrapolations have been carried out to determine accurate thermochemical quantities. Electronic excited states have been calculated with coupled-cluster approaches and also by means of the multireference configuration interaction method.
我们对 CH(n)P 体系中最重要的物种（n = 1-3）进行了高精度的电子结构计算，以对它们进行特征描述，并提供有关平衡和振动平均分子结构、旋转常数、振动频率（谐波和非谐波）、生成焓和垂直激发能的可靠信息。这些化学体系是许多重要反应的中间体，也是典型的磷碳化合物，但它们通常难以通过实验检测到。本研究结果极大地补充了这些化学体系的知识，并可在获得实验信息时作为评估依据。我们使用显式关联耦合簇 RCCSD(T)-F12 方法进行了几何优化和振动频率计算。振动构型相互作用理论用于考虑非谐性效应。基组极限外推法用于确定准确的热化学量。通过耦合簇方法和多参考组态相互作用方法计算了电子激发态。
