Theory of ultrafast process in chemical dynamics

1)利用飞秒时间分辨光电子能谱研究原子核波包在NO2分子圆锥形交叉点上的真实的传输利用两个耦合势能面上的三维量子波包动力学和从头算光电子振幅，从理论上建立了时间分辨光电子能谱及其光电子成像.重点介绍了化学反应动力学的泵浦-探测理论研究的最新进展。我们还提出了一个光学转换的圆锥交叉避免交叉。[Y. Arasaki，K. Takatsuka，K. Wang和V. McKoy，“用角分辨泵浦探测光电子能谱法通过NO2中的锥形相互作用跟踪振动波包动力学”，J. Chem. Phys.接受出版。Yasuki Arasaki和Kazuo Takatsuka，Phys. Chem. Chem. Phys.（Communication），12，1239-1242（2010）.] 2)原子团簇蒸发的一个新的统计理论 ...更多信息 提出了一种新的原子和双原子分子从原子团簇中蒸发的统计理论，其中蒸发的时间尺度与结构异构化的时间尺度竞争。因此，标准的统计理论，如过渡态理论，不能应用。[Mikiya Fujii和Kazuo Takatsuka，J. Chem. Phys.，127，204309（7页）（2007）; Mikiya Fujii和Kazuo Takatsuka，J.Phys.Chem.A111，1389-1402（2007）; Mikiya Fujii和Kazuo Takatsuka，J.Chem.Phys.128，114318（15页）（2008）]。3)经典混沌的量子化机制用我们自己的半经典方法阐明了经典混沌的量子化机制。事实证明，在半经典理论中破坏谱的振幅因子在量子化中并不起主要作用，在数值计算中可以简单地丢弃。[Kazuo Takatsuka，Satoshi Takahashi，Yang Wei Koh和Takefumi Yamashita，J. Chem. Phys.（communication）126，021104（4页）（2007）; Takefumi Yamashita和Kazuo Takatsuka，Prog.理论物理补充。166，56-69（2007）; Satoshi Takahashi和Kazuo Takatsuka，J.Chem.Phys.127，084112（13页）（2007）]。4)关于Born-Oppenheimer近似的有效性我们发现了Born-Oppenheimer近似是如此好的一个近似的原因。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.Phys.124，144101（14页）（2006）。] 5)强激光场中的非绝热电子波包动力学建立了强激光场中电子波包动力学与核运动耦合的从头算理论，并对几个分子系统进行了数值计算。这一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.Chem.Phys.144，93-156，（2009）。Takehiro Yonehara和Kazuo Takatsuka，Chem.Phys.366，114-128（2009）.] 6)建立电子和核波包的非Born-Oppenheimer量子化学将上述电子波包沿分支路径沿着传播和分支核路径的半经典量子化统一为ADF，我们建立了非Born-Oppenheimer电子和核波包动力学的一般实用方案。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。[高冢和夫，实习生。J. Quant。109，2131-2142（2009）中所述。Takehiro Yonehara，Satoshi Takahashi和Kazuo Takatsuka，J.Chem.Phys.130，214113（2009）.] 7)强激光场中的非Born-Oppenheimer量子化学本文推广了非Born-Oppenheimer量子化学理论，使之能处理激光场中的化学反应。[“由于非绝热和强烈的光学相互作用，非玻恩-奥本海默量子化学在飞行中具有连续的路径分支。“Tahehiro Yonehara和Kazuo Takatsuka，J. Chem. Phys. in press（2010）. ] Less

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