A Vibronic Coupling Model to Study the Nonadiabatic Dynamics of Polyenes.

We develop a linear vibronic coupling (LVC) model for polyenes described by the extended Hubbard-Peierls Hamiltonian. This model is applied to -hexatriene to benchmark quantum-classical dynamics methods against fully quantum simulations. We find that surface-hopping methods describe short times more accurately than multitrajectory Ehrenfest. None of the quantum-classical methods studied obtain the long-time population oscillations found in fully quantum simulations. Varying the parameters of the LVC Hamiltonian, we find that surface hopping reproduces the correct trends in the long-time dynamics across a wide range of parameters, but generally overestimates the degree of internal conversion. On the other hand, multitrajectory Ehrenfest gives more accurate long-time populations in proximity to the hexatriene parameter set.