We have developed a novel approach to trajectory surface hopping simulations, termed surface hopping with Ehrenfest excited potential (SHEEP), which offers the possibility to substantially reduce computational cost without significantly degrading accuracy. The crux of our method is a repartitioning of electronic states such that only two potentials can influence the nuclear motion. This is accomplished through representing all excited electronic states as a single average state, and then performing surface hopping between our Ehrenfest excited state and the ground electronic state. These new ideas allow us to perform surface hopping dynamics without any explicit knowledge of excited-state wave functions. Testing on a variety of model problems has revealed that SHEEP is very good at reproducing the population dynamics of standard trajectory surface hopping where all excited states are considered explicitly. Additional computational savings can be obtained if dissipation due to a heat bath is considered.

Surface hopping with Ehrenfest excited potential: Towards accurate and affordable non-adiabatic dynamics for large system

244th National Meeting (2012)

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