Surface hopping with a manifold of electronic states. I. Incorporating surface-leaking to capture lifetimes
Abstract
We investigate the incorporation of the surface-leaking (SL) algorithm into Tully’s fewest-switches surface hopping (FSSH) algorithm to simulate some electronic relaxation induced by an electronic bath in conjunction with some electronic transitions between discrete states. The resulting SL-FSSH algorithm is benchmarked against exact quantum scattering calculations for three one-dimensional model problems. The results show excellent agreement between SL-FSSH and exact quantum dynamics in the wide band limit, suggesting the potential for a SL-FSSH algorithm. Discrepancies and failures are investigated in detail to understand the factors that will limit the reliability of SL-FSSH, especially the wide band approximation. Considering the easiness of implementation and the low computational cost, we expect this method to be useful in studying processes involving both a continuum of electronic states (where electronic dynamics are probabilistic) and processes involving only a few electronic states (where non-adiabatic processes cannot ignore short-time coherence).
Document Details
- Document Type
- Pub Defense Publication
- Publication Date
- Feb 25, 2015
- Source ID
- 10.1063/1.4908032
Entities
People
- Joseph E Subotnik
- Wenjie Dou
- Wenjun Ouyang
Organizations
- Air Force Office of Scientific Research
- University of Pennsylvania