Simultaneous-trajectory surface hopping: A parameter-free algorithm for implementing decoherence in nonadiabatic dynamics

Journal Article · Sat Jan 01 04:00:00 EST 2011 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3575588· OSTI ID:1065696

Shenvi, Neil ^[1]; Subotnik, Joseph E. ^[2]; Yang, Weitao ^[1]

---

1. Duke Univ., Durham, NC (United States)
2. Univ. of Pennsylvania, Philadelphia, PA (United States)

In this paper, we introduce a trajectory-based nonadiabatic dynamics algorithm which aims to correct the well-known overcoherence problem in Tully's popular fewest-switches surface hopping algorithm. Our simultaneous-trajectory surface hopping algorithm propagates a separate classical trajectory on each energetically accessible adiabatic surface. The divergence of these trajectories generates decoherence, which collapses the particle wave function onto a single adiabatic state. Decoherence is implemented without the need for any parameters, either empirical or adjustable. We apply our algorithm to several model problems and find a significant improvement over the traditional algorithm.

• Research Organization: Energy Frontier Research Centers (EFRC); Center for Solar Fuels (UNC EFRC)
• Sponsoring Organization: USDOE SC Office of Basic Energy Sciences (SC-22)
• DOE Contract Number: SC0001011
• OSTI ID: 1065696
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 14 Vol. 134 (14); ISSN 0021-9606
• Publisher: American Institute of Physics (AIP)
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
catalysis (heterogeneous)
catalysis (homogeneous)
charge transport
electrodes - solar
hydrogen and fuel cells
materials and chemistry by design
photosynthesis (natural and artificial)
solar (fuels)
solar (photovoltaic)
synthesis (novel materials)
synthesis (self-assembly)