Theory of ultrafast process in chemical dynamics

化学动力学超​​快过程理论

• 批准号: 18066004
• 负责人: TAKATSUKA Kazuo
• 金额: $ 21.89万
• 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 on Priority Areas
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2009
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-18066004/
• 关键词: 化学反応論; 超高速動力学; レーザー化学; 分子動力学

1) Femtosecond time-resolved photoelectron spectroscopy study on real time passage of nuclear wave packets across the conical intersection of NO2Time-resolved photoelectron spectroscopy and its photoelectron imaging are theoretically produced in terms of three dimensional quantum wavepacket dynamics on two coupled potential energy surfaces along with ab initio photoelectron amplitudes. This highlights the current progress of theoretical studies in pump-probe studies on chemical reaction dynamics. We have also proposed an optical conversion of the conical intersection to an avoided crossing.[Y. Arasaki, K. Takatsuka, K. Wang, and V. McKoy, "Tracking vibrational wavepacket dynamics through a conical interaction in NO2 with angle-resolved pump-probe photoelectron spectroscopy", J. Chem. Phys. accepted for publication. Yasuki Arasaki and Kazuo Takatsuka, Phys. Chem. Chem. Phys. (Communication), 12, 1239-1242 (2010).]2) A new statistical theory of evaporation from atomic clustersWe have dev … More eloped a new statistical theory of atomic and diatomic molecule evaporation from an atomic cluster, in which the time scale of evaporation competes with that of structural isomerization. Therefore the standard statistical theory such as the transition state theory, cannot be applied.[Mikiya Fujii and Kazuo Takatsuka, J. Chem. Phys., 127, 204309 (7 pages) (2007); Mikiya Fujii and Kazuo Takatsuka, J. Phys. Chem. A 111, 1389-1402 (2007); Mikiya Fujii and Kazuo Takatsuka, J. Chem. Phys. 128, 114318 (15 pages) (2008).]3) Mechanism of quantization of classical chaosMechanism of quantization of classical chaos has been clarified through our own semiclassical approach. It turns out that the amplitude factor that destroys the spectrum in semiclassical theory does not play a major role in quantization and can be simply discarded in numerical calculations.[Kazuo Takatsuka, Satoshi Takahashi, Yang Wei Koh, and Takefumi Yamashita, J. Chem. Phys. (communication) 126, 021104 (4 pages) (2007); Takefumi Yamashita and Kazuo Takatsuka, Prog. Theoret. Phys. Supplement. 166, 56-69 (2007); Satoshi Takahashi and Kazuo Takatsuka, J. Chem. Phys. 127, 084112 (13 pages) (2007).]4) On the validity of the Born-Oppenheimer approximationWe have found why the Born-Oppenheimer approximation is so good an approximation. The error contained is proportional to the power of 1.5 of m/M, where m and M are the mass of electron and nuclei, respectively.[Satoshi Takahashi and Kazuo Takatsuka, J. Chem. Phys. 124, 144101 (14 pages) (2006).]5) Nonadiabatic electron wavepacket dynamics in intense laser fieldAn ab inito theory for electron wavepacket dynamics coupled with nuclear motion in intense laser field has been formulated, and numerically applied to several molecular systems. This theory sets a theoretical foundation with which to control chemical reactions through the control of electronic states.[Kazuo Takatsuka and Takehiro Yonehara, Adv. Chem. Phys. 144, 93-156, (2009). Takehiro Yonehara and Kazuo Takatsuka, Chem. Phys. 366, 114-128 (2009).]6) Establishing non-Born-Oppenheimer quantum chemistry for electronic and nuclear wavepacketsUnifying the above electron wavepacket propagated along the branching paths and the semiclassical quantization of the branching nuclear path in terms ADF, we have formulated our general and practical scheme of non-Born-Oppenheimer electronic and nuclear wavepacket dynamics. The theory has been actually implemented in GAMESS code and numerically tested. We are now in a new stage of quantum chemistry for excited states.[Kazuo Takatsuka, Intern. J. Quant. Chem. 109, 2131-2142 (2009). Takehiro Yonehara, Satoshi Takahashi and Kazuo Takatsuka, J. Chem. Phys. 130, 214113 (2009).]7) Non-Born-Oppenheimer quantum chemistry in intense laser fieldsThe theory of non-Born-Oppenheimer quantum chemistry has been generalized so as to be able to treat chemical reactions in laser fields.[“Non-Born-Oppenheimer quantum chemistry on the fly with continuous path branching due to nonadiabatic and intense optical interactions." Tahehiro Yonehara and Kazuo Takatsuka, J. Chem. Phys. in press (2010). ] Less

1）飞秒时间分辨光电子能谱研究核波包穿过NO2圆锥形交叉点的实时通过时间分辨光电子能谱及其光电子成像理论上是根据两个耦合势能表面上的三维量子波包动力学以及从头算光电子振幅产生的。这凸显了当前化学反应动力学泵探针研究的理论研究进展。我们还提出了将圆锥形交叉点光学转换为避免交叉点的方案。[Y. Arasaki、K. Takatsuka、K. Wang 和 V. McKoy，“利用角分辨泵浦探针光电子能谱通过 NO2 中的锥形相互作用跟踪振动波包动力学”，J. Chem。物理。接受出版。 Yasuki Arasaki 和 Kazuo Takatsuka，物理学家。化学。化学。物理。 (通讯), 12, 1239-1242 (2010).]2) 原子团簇蒸发的新统计理论我们开发了一种原子团簇中原子和双原子分子蒸发的新统计理论，其中蒸发的时间尺度与结构异构化的时间尺度竞争。因此，不能应用标准统计理论，例如过渡态理论。 [Mikiya Fujii and Kazuo Takatsuka, J. Chem. Phys.，127, 204309（7 页）（2007 年）； Mikiya Fujii 和 Kazuo Takatsuka，J. Phys。化学。 A 111, 1389-1402 (2007)； Mikiya Fujii 和 Kazuo Takatsuka，J. Chem。物理。 128, 114318 (15 页) (2008).]3) 经典混沌的量子化机制经典混沌的量子化机制已经通过我们自己的半经典方法得到了阐明。事实证明，半经典理论中破坏频谱的振幅因子在量子化中并不起主要作用，可以在数值计算中简单地丢弃。 [Kazuo Takatsuka, Satoshi Takahashi, Yang Wei Koh, and Takefum​​i Yamashita, J. Chem.物理。 （通讯）126、021104（4页）（2007年）；山下武文和高冢一夫，Prog。理论。物理。补充。 166, 56-69 (2007); Satoshi Takahashi 和 Kazuo Takatsuka，J. Chem。物理。 127, 084112 (13 页) (2007).]4) 关于 Born-Oppenheimer 近似的有效性我们已经发现了为什么 Born-Oppenheimer 近似是一个很好的近似。所包含的误差与 m/M 的 1.5 次方成正比，其中 m 和 M 分别是电子和原子核的质量。 [Satoshi Takahashi 和 Kazuo Takatsuka, J. Chem.物理。 124, 144101 (14 页) (2006).]5) 强激光场中的非绝热电子波包动力学 强激光场中电子波包动力学与核运动耦合的从头理论已经被表述出来，并在数值上应用于几个分子系统。该理论为通过控制电子态来控制化学反应奠定了理论基础。 [Kazuo Takatsuka 和 Takehiro Yonehara, Adv.化学。物理。 144, 93-156, (2009)。 Takehiro Yonehara 和 Kazuo Takatsuka，化学。物理。 366, 114-128 (2009).]6) 建立电子和核波包的非玻恩-奥本海默量子化学将上述沿分支路径传播的电子波包和分支核路径的半经典量子化统一为ADF，我们制定了非玻恩-奥本海默电子和核波包动力学的通用且实用的方案。该理论已在 GAMESS 代码中实际实现并进行了数值测试。我们现在处于激发态量子化学的新阶段。[Kazuo Takatsuka，实习生。 J. Quant.化学。 109, 2131-2142 (2009)。 Takehiro Yonehara、Satoshi Takahashi 和 Kazuo Takatsuka，J. Chem。物理。 130, 214113 (2009).]7) 强激光场中的非玻恩-奥本海默量子化学非玻恩-奥本海默量子化学理论已得到推广，以便能够处理激光场中的化学反应。[“由于非绝热和强光相互作用，动态非玻恩-奥本海默量子化学具有连续路径分支。” Tahehiro Yonehara 和 Kazuo Takatsuka，J. Chem。物理。正在出版（2010）。 ] 较少的

项目成果

Optical conversion of conical intersection to avoided crossing

圆锥形交叉点的光学转换为避免交叉点

• 发表时间: 2010
• 期刊: Phys.Chem.Chem.Phys. 12
• 作者: Yasuki Arasaki;Kazuo Takatsuka
• 通讯作者: Kazuo Takatsuka

ホルムアミドの互変異性化反応における電子ダイナミクス

甲酰胺互变异构反应中的电子动力学

• 发表时间: 2009
• 作者: 長島謙吾;高塚和夫
• 通讯作者: 高塚和夫

Energy quantization of chaos with the semiclassical phases alone.

仅半经典相的混沌能量量子化。

• 发表时间: 2007
• 期刊: J. Chem. Phys. (communication) 126
• 作者: K. Takatsuka;S. Takahashi;Y.W. Koh;T. Yamashita
• 通讯作者: T. Yamashita

Temperature and heat capacity of atomic clusters as estimated in terms of kinetic-energy release of atomic evaporation

根据原子蒸发的动能释放估算原子团簇的温度和热容

• 发表时间: 2007
• 期刊: J. Chem. Phys. 127
• 作者: H. Ushiyama;K. Takatsuka;M.Sasai;Yang Wei Koh and Kazuo Takatsuka;加藤重樹;中野雅由;M. Sasai;Shigeki Kato;Mikiya Fujii and Kazuo Takatsuka
• 通讯作者: Mikiya Fujii and Kazuo Takatsuka

非断熱遷移動力学を伴う超高齢力学理論

具有非绝热转变动力学的超时效动力学理论

• 发表时间: 2009
• 作者: 米原丈博;高塚和夫
• 通讯作者: 高塚和夫