Department of Information Technology, University of Debrecen , P.O. Box 12, H-4010 Debrecen, Hungary.
J Phys Chem A. 2013 Sep 12;117(36):8497-505. doi: 10.1021/jp311014z. Epub 2013 Jan 16.
We follow a suggestion by Lipoff and Herschbach (Mol. Phys. 2010, 108, 1133) and compare dressed potentials to get insight regarding the low-energy dynamics (e.g., cold reaction) taking place in molecular systems. In this particular case we are interested in studying the effect of topological effects on the interacting atoms. For this purpose we consider dressed adiabatic and adiabatic-via-dressed diabatic potentials in the entrance channel of reactive systems. In a recent study of this kind for the F + H2 system (J. Chem. Phys. 2012, 136, 054104), we revealed that a single Jahn-Teller conical intersection is expected to have only a mild effect on the dynamics. This fact implies that the Born-Oppenheimer approximation is expected to be valid for this system at least for low enough energies. In the present article this study is extended to include also the Renner-Teller effect as produced by the two lower degenerate Π states. As a result we consider three electronic states which enforce the use of the adiabatic-to-diabatic transformation (ADT) matrix A. The results indicate that the topological effects as produced by the extended Renner/Teller-Jahn/Teller system are strong to the level that, most likely, abolishes the Born-Oppenheimer approximation for this system, all this in contrast to our previous findings (see above publication).
我们遵循 Lipoff 和 Herschbach 的建议（Mol. Phys. 2010, 108, 1133），通过比较修饰势来深入了解分子系统中发生的低能动力学（例如冷反应）。在这种特殊情况下，我们有兴趣研究拓扑效应对相互作用原子的影响。为此，我们在反应体系的入口通道中考虑了修饰的绝热和绝热-通过修饰的非绝热势。在最近对 F + H2 体系的研究中（J. Chem. Phys. 2012, 136, 054104），我们揭示了单个 Jahn-Teller 锥形交叉点预计对动力学只有轻微影响。这一事实意味着，对于至少足够低的能量，Born-Oppenheimer 近似对于该体系是有效的。在本文中，这项研究扩展到包括由两个较低简并Π态产生的 Renner-Teller 效应。结果，我们考虑了三个电子态，这要求使用绝热到非绝热变换（ADT）矩阵 A。结果表明，由扩展的 Renner/Teller-Jahn/Teller 系统产生的拓扑效应非常强烈，以至于很可能为该体系取消 Born-Oppenheimer 近似，这与我们之前的发现（见上述出版物）形成对比。
