We apply a recently proposed ring-polymer surface hopping (RPSH) approach to investigate the real-time non-adiabatic dynamics with explicit nuclear quantum effects. The non-adibatic electronic transitions are described through Tully's fewest switches surface-hopping (FSSH) algorithm and the nuclei are quantized through ring-polymer Hamiltonian in an extended phase-space. Using Tully's single and dual avoided crossing models we prove that tunnelling and zero point energy are explicitly included in the nonadiabatic dynamics simulations leading to a substantial improvement of the branching probabilities of forward/backward scattering in the low and moderate momentum regions. In the context of Tully's model of extended coupling with reflection, we show that RPSH can capture decoherence yielding reflection probabilities that are very close to the exact calculations. Moreover, studying coupled Morse potential models that are parametrized to describe photodissociation process, we show that RPSH captures both short-time non-adiabatic behaviour and long-term branching ratios. These promising results demonstrate the potential of RPSH as an efficient method to incorporate nuclear quantum effects into the non-adiabatic dynamics simulations in condensed-phase systems.

Ring-polymer surface-hopping: Incorporating nuclear quantum effects into non-adiabatic dynamics simulations

254th National Meeting (2017)

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