Electronically nonadiabatic wave packet propagation using frozen Gaussian scattering

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Abstract
We present an approach, which allows to employ the adiabatic wave packet propagation technique and semiclassical theory to treat the nonadiabatic processes by using trajectory hopping. The approach developed generates a bunch of hopping trajectories and gives all additional information to incorporate the effect of nonadiabatic coupling into the wave packet dynamics. This provides an interface between a general adiabatic frozen Gaussian wave packet propagation method and the trajectory surface hopping technique. The basic idea suggested in [A. D. Kondorskiy and H. Nakamura, J. Chem. Phys. 120, 8937 (2004)] is revisited and complemented in the present work by the elaboration of efficient numerical algorithms. We combine our approach with the adiabatic Herman-Kluk frozen Gaussian approximation. The efficiency and accuracy of the resulting method is demonstrated by applying it to popular benchmark model systems including three Tully’s models and 24D model of pyrazine. It is shown that photoabsorption spectrum is successfully reproduced by using a few hundreds of trajectories. We employ the compact finite difference Hessian update scheme to consider feasibility of the ab initio “on-the-fly” simulations. It is found that this technique allows us to obtain the reliable final results using several Hessian matrix calculations per trajectory.
Funding Information
  • Ministry of Education, Culture, Sports, Science, and Technology (23224013, 26248038)
  • Russian Foundation for Basic Research (13-08-01193)

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