Ring Polymer Surface Hopping: Incorporating Nuclear Quantum Effects into Nonadiabatic Molecular Dynamics Simulations

5 years ago

Ring Polymer Surface Hopping: Incorporating Nuclear Quantum Effects into Nonadiabatic Molecular Dynamics Simulations

Farnaz A. Shakib, Pengfei Huo

We apply a recently proposed ring polymer surface hopping (RPSH) approach to investigate the real-time nonadiabatic dynamics with explicit nuclear quantum effects. The nonadibatic electronic transitions are described through Tully’s fewest-switches surface hopping algorithm and the motion of the nuclei are quantized through the ring polymer Hamiltonian in the extended phase space. Applying the RPSH method to simulate Tully’s avoided crossing models, we demonstrate the critical role of the nuclear tunneling effect and zero-point energy for accurately describing the transmission and reflection probabilities with low initial momenta. In addition, in Tully’s extended coupling model, we show that the ring polymer quantization effectively captures decoherence, yielding more accurate reflection probabilities. These promising results demonstrate the potential of using RPSH as an accurate and efficient method to incorporate nuclear quantum effects into nonadiabatic dynamics simulations.

Publisher URL: http://dx.doi.org/10.1021/acs.jpclett.7b01343

DOI: 10.1021/acs.jpclett.7b01343