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

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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