Basic theories for molecular quantum dynamics

分子量子动力学基础理论

• 批准号: 15205003
• 负责人: TAKATSUKA Kazuo
• 金额: $ 28.87万
• 依托单位: The University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15205003/
• 关键词: Quantum chaos; wavepacket dynamics; proton transfer; electron dynamics; cluster; 量子動力学; 内部空間

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.

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)阐明了分子振动态经典混沌的量子化机制。这被称为相位量化。为了计算混沌状态下的量子化能量，我们基于已经发现的量子化机制，提出了一种简单而常规的方法。我们一直在开发能量、时间和角度分辨光电子能谱的从头算方法。以NaI分子为例，我们已经证明，在飞秒泵浦探针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tropolone质子转移的一系列研究中，我们发现了质子转移诱导的互变异构与超共轭耦合的化学远程相互作用，导致甲基的内旋。这为通过电子结构变化的确定性动力学设定了一个重要的例子，这与混沌（所谓的分子内振动能量再分配）引起的随机动力学形成了对比。4)以强激光场最终控制分子电子态为目标，建立了阿秒时间尺度下电子波包动力学的理论基础，并通过运动学耦合（非玻恩-奥本海默相互作用）与经典核运动耦合。所有这些，连同其他未在这里提出的结果，已经以系统的方式进一步发展。

项目成果

Temperature, geometry, and variational statistical structure in microcanonical ensemble for structural isomerization dynamics of clusters : A multichannel chemical reaction beyond the transition-state concept.

用于簇结构异构化动力学的微正则系综中的温度、几何形状和变分统计结构：超越过渡态概念的多通道化学反应。

• 发表时间: 2005
• 期刊: Adv. Chem. Phys. 130
• 作者: Matsumoto;D.;F.Masuda;Kazuo Takatsuka
• 通讯作者: Kazuo Takatsuka

Semiclassical quantization of chaos in terms of an amplitude-free quasi-correlation function.

用无幅准相关函数对混沌进行半经典量化。

• 发表时间: 2003
• 期刊: J. Phys. A : Gen. Math. 36
• 作者: K.Hotta;K.Takatsuka
• 通讯作者: K.Takatsuka

Effect of an intrinsic of molecular internal space on chemical reaction dynamics.

分子内部空间本征对化学反应动力学的影响。

• 发表时间: 2004
• 期刊: Adv.Chem.Phys. 130
• 作者: Tomohiro Yanao;Kazuo Takatsuka
• 通讯作者: Kazuo Takatsuka

H.Ushiyama, K.Takatsuka: "Time-dependent quasi-semiclassical approach for tunneling chemical reactions"J.Chem.Phys.. 120. 4561-4572 (2004)

H.Ushiyama, K.Takatsuka：“隧道化学反应的时间相关准半经典方法”J.Chem.Phys.. 120. 4561-4572 (2004)

Temperature, geometry, and variational structure in microcanonical ensemble for structural isomerization dynamics of clusters : A multichannel chemical reaction beyond the transition-state concent

用于簇结构异构化动力学的微正则系综中的温度、几何形状和变分结构：超越过渡态浓度的多通道化学反应

• 发表时间: 2005
• 期刊: Adv.Chem.Phys. 130
• 作者: Takeshi Mizunoya;Katsuhiro Sakurai;Riki Morioka;Yoshiro Higano;Hisashi Hayashi;K.Takatsuka
• 通讯作者: K.Takatsuka