Department of Chemistry, University of Calcutta, Kolkata-700009, India.
J Chem Phys. 2012 Feb 7;136(5):054104. doi: 10.1063/1.3679406.
We follow a suggestion by Lipoff and Herschbach [Mol. Phys. 108, 1133 (2010)] and compare dressed and bare adiabatic 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 to study the effect of conical intersections (ci) on the interacting atoms. For this purpose, we consider vibrational dressed adiabatic and vibrational dressed diabatic potentials in the entrance channel of reactive systems. According to our study, the most one should expect, in case of F + H(2), is a mild effect of the (1, 2) ci on its reactive/exchange process--an outcome also supported by experiment. This happens although the corresponding dressed and bare potential barriers (and the corresponding van der Waals potential wells) differ significantly from each other.
我们遵循 Lipoff 和 Herschbach 的建议[Mol. Phys. 108, 1133 (2010)]，通过比较 dressed 和 bare 绝热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，我们有兴趣研究锥形交叉（ci）对相互作用原子的影响。为此，我们在反应性系统的入口通道中考虑了振动 dressed 绝热和振动 dressed 非绝热势。根据我们的研究，在 F + H(2)的情况下，最应该预期的是（1, 2）ci 对其反应/交换过程的轻微影响——这一结果也得到了实验的支持。尽管相应的 dressed 和 bare 势垒（以及相应的范德华势阱）彼此之间存在显著差异，但确实发生了这种情况。
