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Studies of Non-adiabatic Chemical Dynamics based on the Zhu-Nakamura Theory

基于Zhu-Nakamura理论的非绝热化学动力学研究

基本信息

批准号：
15002011
负责人：
NAKAMURA Hiroki
金额：
$ 212.16万
依托单位：
Institute for Molecular Science (2004-2005)Okazaki National Research Institutes (2003)
依托单位国家：
日本
项目类别：
Grant-in-Aid for Specially Promoted Research
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

项目摘要

The trajectory surface hopping method and semiclassical frozen Gaussian propagation method have been generalized so that they can take into account classically forbidden nonadiabatic transitions and tunneling effects and can be applied to large dimensional systems. A new semiclassical optimal laser control theory has been developed based on the method and the quadratic chirping method has also been developed successfully to make excitation processes highly efficient. The Zhu-Nakamura formulas have been successfully incorporated into the Marcus type theory of electron transfer and it has become possible to treat the processes correctly no matter how strong the electronic coupling is. This theory can be applied to multi-dimensional systems. New efficient theories have been developed for tunneling splitting in symmetric double well potentials and decay of metastable states through tunneling. A new efficient method to detect caustics in multi-dimensional systems has also been formulated. T … More his makes possible to take into account the tunneling effects in classical trajectory method. The above mentioned theories have been successfully applied not only to model systems but also to real molecular systems. Examples are OHCl reaction, N_2O photo-dissociation, isomerization of retinal, hydrogen transmission through five-membered ring of corannulenyl radical, photo-chromic conversion between cyclohexadiene and hexatriene, and laser control of isomerization of HCN. The tunnel splitting theory has been applied to malonaldehyde, vinyl radical, and formic acid dimmer, and good agreements have been obtained with experiments. Experimentally, molecular beam machines of very high precision have been developed and fruitful collaborations with theory have been carried out.In summary, new powerful theories and methods have been developed to promote future studies for understanding large scale nonadiabatic chemical dynamics, laser control of realistic molecular systems, and development and control of molecular functions. Less

本文推广了轨道表面跳跃方法和半经典冻结高斯传播方法，使它们能考虑经典禁戒的非绝热跃迁和隧穿效应，并能应用于高维系统。在此基础上发展了一种新的半经典最优激光控制理论，并成功地发展了二次啁啾方法，使激发过程高效化。Zhu-Nakamura公式已成功地纳入电子转移的Marcus型理论中，并且无论电子耦合有多强，都可以正确地处理过程。这个理论可以应用于多维系统。对于对称双势阱中的隧穿劈裂和亚稳态的隧穿衰变，人们提出了新的有效理论。提出了一种新的有效的多维焦散线检测方法。不 ...更多信息这使得在经典轨迹法中考虑隧道效应成为可能。上述理论不仅成功地应用于模型体系，而且也应用于真实的分子体系。如OHCl反应、N_2O光解、视黄醛异构化、氢通过角轮烯基五元环的传递、环己二烯与己三烯的光致变色转化、HCN异构化的激光控制等。将隧道劈裂理论应用于丙二醛、乙烯基自由基和甲酸二聚体，得到了与实验符合较好的结果。在实验方面，高精度的分子束装置已经研制成功，并与理论进行了卓有成效的合作，为理解大尺度非绝热化学动力学、激光控制现实分子系统、开发和控制分子功能等方面的研究提供了新的理论和方法。少