In the traditional fewest switches surface hopping (FSSH), trivial crossings between uncoupled or weakly coupled states have highly peaked nonadiabatic couplings and thus are difficult to deal with in the preferred, adiabatic representation. Here, we classify surface crossings into four general types and propose a parameter-free crossing corrected FSSH (CC-FSSH) algorithm, which could treat multiple trivial crossings within a time interval. As examples, Holstein Hamiltonians with different parameters are adopted to mimic electron dynamics in tens to hundreds of molecules, which suffer from severe trivial crossing problems. Using existed surface hopping approaches as references, we show that CC-FSSH exhibits significantly fast time interval convergence and weak system size dependence. In all cases, a reliable description is achieved with a large time interval of 1 fs. With a simple formalism and the ability to describe complex surface crossings, CC-FSSH could potentially simulate general nonadiabatic dynamics in nanoscale materials with a high efficiency.
We provide an in-depth investigation of the time interval convergence when both trivial crossing and decoherence corrections are applied to Tully's fewest switches surface hopping (FSSH) algorithm. Using one force-based and one energy-based decoherence strategies as examples, we show decoherence corrections intrinsically enhance the trivial crossing problem. We propose a restricted decoherence (RD) strategy and incorporate it into the self-consistent (SC) fewest switches surface hopping algorithm [L. Wang and O. V. Prezhdo, J. Phys. Chem. Lett. 5, 713 (2014)]. The resulting SC-FSSH-RD approach is applied to general Hamiltonians with different electronic couplings and electron-phonon couplings to mimic charge transport in tens to hundreds of molecules. In all cases, SC-FSSH-RD allows us to use a large time interval of 0.1 fs for convergence and the simulation time is reduced by over one order of magnitude. Both the band and hopping mechanisms of charge transport have been captured perfectly. SC-FSSH-RD makes surface hops in the adiabatic representation and can be implemented in both diabatic and locally diabatic representations for wave function propagation. SC-FSSH-RD can potentially describe general nonadiabatic dynamics of electrons and excitons in organics and other materials.
We
present a subspace surface hopping strategy to deal with complex
surface crossings in nonadiabatic dynamics. By focusing on only important
adiabatic states, we make subspace crossing correction (SCC) in the
framework of the standard fewest switches surface hopping (FSSH) and
the global flux surface hopping (GFSH). The resulting SCC-FSSH and
SCC-GFSH approaches show much better performance than the counterparts
using all adiabatic states for surface hopping. As demonstrated in
a series of Holstein models with up to over 1000 molecular sites,
both SCC-FSSH and SCC-GFSH show excellent size independence with a
large time step size of 1 fs. Especially, SCC-GFSH does not refer
to nonadiabatic couplings at all and gives a more proper description
of superexchange, and thus, it is promising for realistic applications
with complex potential energy surfaces.
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