Abstract It is now confirmed that the Zhu–Nakamura (ZN) theory of nonadiabatic transition is useful to investigate various nonadiabatic chemical dynamics. The theory, being one-dimensional, presents a whole set of analytical formulas that enables us to treat the dynamics efficiently. It is also quite significant that classically forbidden transitions can be dealt with analytically. The theory can be combined with the trajectory surface hopping (TSH) method (ZN-TSH) and is demonstrated to be useful to clarify the dynamics of not only simple tri-atomic reactions but also large chemical systems. The whole set of analytical formulas directly applicable to practical systems is summarised and the applications to polyatomic systems are illustrated. Examples of polyatomic molecules are , , indolylmaleimide, cyclohexadiene (CHD), and retinal. The Fortran code for the whole set of ZN formulas is provided in Appendix for the convenience of a reader who is interested in using them. The ZN-TSH method can be combined with the QM/MM method to clarify reaction dynamics in the surrounding environment. This is named as ZN-QM/MM-TSH. The particle-mesh Ewald (PME) method can also be combined with ZN-TSH to clarify reaction dynamics in solutions. This is named as ZN-PME-TSH. Formulations of these methods are presented together with practical applications. Examples treated by ZN-QM/MM-TSH are photoisomerization dynamics of retinal chromophore embedded in the protein environment. The differences in the isomerization mechanisms between rhodopsin and isorhodopsin are made clear. The faster and more efficient isomerization of rhodopsin compared to isorhodopsin is nicely reproduced. Examples of reactions in solutions are photoisomerizations of retinal and CHD. The experimentally observed long life time of the excited state of retinal is reproduced and is found to be due to the long-range solvation effect. The solvent dependent branching ratios of CHD:hexatriene (HT) are clarified for the ethanol and hexane solvents by the ZN-PME-TSH method. Both ZN-QM/MM-TSH and ZN-PME-TSH are thus demonstrated to be promising methods to deal with a wide range of nonadiabatic dynamics in large chemical and biological systems.

中文翻译：

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通过非绝热转变的朱-中村理论阐明非绝热化学动力学：从三原子系统到溶液中的反应

摘要 现在已经证实，非绝热转变的朱-中村 (ZN) 理论可用于研究各种非绝热化学动力学。该理论是一维的，提供了一整套分析公式，使我们能够有效地处理动力学。可以分析处理经典禁止的转换也非常重要。该理论可以与轨迹表面跳跃 (TSH) 方法 (ZN-TSH) 相结合，并被证明可用于阐明简单的三原子反应和大型化学系统的动力学。总结了一整套直接适用于实际系统的分析公式，并说明了在多原子系统中的应用。多原子分子的例子是，，，吲哚基马来酰亚胺，环己二烯（CHD）和视黄醛。为方便有兴趣使用它们的读者，附录中提供了整套 ZN 公式的 Fortran 代码。ZN-TSH 方法可以与 QM/MM 方法结合，以阐明周围环境中的反应动力学。这被命名为 ZN-QM/MM-TSH。粒子网格 Ewald (PME) 方法也可以与 ZN-TSH 结合以阐明溶液中的反应动力学。这被命名为 ZN-PME-TSH。这些方法的配方与实际应用一起呈现。ZN-QM/MM-TSH 处理的例子是嵌入蛋白质环境中的视网膜发色团的光异构化动力学。明确了视紫红质和异视紫质之间异构化机制的差异。与异视紫红质相比，视紫质的异构化速度更快、效率更高，得到了很好的再现。溶液中反应的例子是视黄醛和 CHD 的光异构化。实验观察到的视网膜激发态的长寿命被重现，并被发现是由于长程溶剂化效应。对于乙醇和己烷溶剂，通过 ZN-PME-TSH 方法阐明了 CHD:己三烯 (HT) 的溶剂相关支化比。因此，ZN-QM/MM-TSH 和 ZN-PME-TSH 都被证明是处理大型化学和生物系统中各种非绝热动力学的有前途的方法。用 ZN-PME-TSH 方法对乙醇和己烷溶剂中的己三烯 (HT) 进行澄清。因此，ZN-QM/MM-TSH 和 ZN-PME-TSH 都被证明是处理大型化学和生物系统中各种非绝热动力学的有前途的方法。用 ZN-PME-TSH 方法对乙醇和己烷溶剂中的己三烯 (HT) 进行澄清。因此，ZN-QM/MM-TSH 和 ZN-PME-TSH 都被证明是处理大型化学和生物系统中各种非绝热动力学的有前途的方法。