Schild Axel, Paulus Beate
Freie Universität Berlin, Institut für Chemie und Biochemie, Takustr. 3, 14195 Berlin, Germany.
J Comput Chem. 2013 Jun 15;34(16):1393-7. doi: 10.1002/jcc.23273. Epub 2013 Mar 18.
We present multireference calculations for the characterization of ring inversion and double bond shifting in cyclooctatetraene. The results show that it is necessary to treat the dynamical correlation very accurately to obtain correct values for the barrier heights. This can be done, for example, with multireference configuration interaction or with perturbation theory of third order. However, detailed analysis also shows that already a complete active space self-consistent field treatment describes the processes surprisingly well. Thus, this method could be used as a computationally cheap method, for example, for dynamics simulations.
我们给出了用于表征环辛四烯中环反转和双键移动的多参考计算。结果表明，为了获得正确的势垒高度值，必须非常精确地处理动态相关性。例如，可以通过多参考组态相互作用或三阶微扰理论来做到这一点。然而，详细分析还表明，即使是完全活性空间自洽场处理也能令人惊讶地很好描述这些过程。因此，这种方法可以用作一种计算成本低的方法，例如用于动力学模拟。
