Basic theories for molecular quantum dynamics

我们发展了以下理论，这些理论对分子科学的基本进展都是至关重要的。1)我们阐明了分子振动态中经典混沌的量子化机制。这被称为相位量子化。为了计算混沌区域的量子化能量，我们在我们发现的量子化机制的基础上提出了一种简单而常规的方法。2)我们一直在发展能量、时间和角度分辨光电子能谱的从头算方法。以NaI分子为例，我们证明了在飞秒泵浦探测光电子能谱中确实可以观察到分子内电子转移引起的波包分叉。3)在我们对5-甲基托普罗酮质子转移的一系列研究中，我们发现了一个化学长程相互作用，即质子转移诱导的互变异构化和超共轭作用的耦合，从而导致甲基的内旋。这是通过电子结构的变化来确定动力学的一个重要例子，而不是由于混沌引起的随机动力学(所谓的分子内振动能量重新分配)。4)为了通过强激光场最终控制分子的电子态，我们建立了阿秒时间尺度下的电子波包动力学的理论基础，它通过运动学耦合(非Born-Oppenheimer相互作用)与经典的核运动耦合。所有这些以及其他没有在这里提出的结果都得到了系统的发展。

We have developed the following theories that are all vital to the fundamental progress of molecular science.1)We have clarified the mechanism of quantization of classical chaos in molecular vibrations states. This is called phase-quantization. To calculate the quantized energy in chaotic regime, we have proposed a simple and conventional method based on our found mechanism of quantizations.2)We have been developing ab initio method for energy-, time-, and angle- resolved photoelectron spectroscopy. As an example, taking NaI molecule, we have shown that the wavepacket bifurcation due to intramolecular electron transfer can be indeed observed in femtosecond pump-probe photoelectron spectroscopy.3)In a series of our studies on proton transfer in 5-methyl tropolone, we have found a chemical long-range interaction in terms of the coupling of tautomerization induced by proton transfer and the hyperconjugation, which causes the internal rotation of the methyl group. This sets an important example of deterministic dynamic via the change of electronic structure, which is in contrast to stochastic dynamics due to chaos (the so-call intramolecular vibrational energy redistribution.)4)Aiming for the eventual control of molecular electronic states by means of intense laser field, we have set a theoretical foundation of electron wavepacket dynamics in the attosecond time scale, which couples with classical nuclear motion through the kinematic coupling (the non-Born-Oppenheimer interaction).All these along with other results not presented here have been further developed in a systematic way.