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Strong Influence of Decoherence Corrections and Momentum Rescaling in Surface Hopping Dynamics of Transition Metal Complexes

preprint
submitted on 29.05.2019 and posted on 30.05.2019 by Felix Plasser, Sebastian Mai, Maria Fumanal, Etienne Gindensperger, Chantal Daniel, Leticia Gonzalez
The reliability of different parameters in the surface hopping method is assessed for a vibronic coupling model of a challenging transition metal complex, where a large number of electronic states of different multiplicities are met within a small energy range. In particular, the effect of two decoherence correction schemes and of various strategies for momentum rescaling and treating frustrating hops during the dynamics is investigated and compared against an accurate quantum dynamics simulation. The results show that small differences in the surface hopping protocol can strongly affect the results. We find a clear preference for momentum rescaling along the nonadiabatic coupling vector and trace this effect back to an enhanced number of frustrated hops. Furthermore, reflection of the momentum after frustrated hops is shown to work better than to ignore the process completely. The study also highlights the importance of the decoherence correction but neither of the two methods employed, energy based decoherence and augmented fewest switches surface hopping, performs completely satisfactory. More generally, the study emphasises the importance of the often neglected parameters in surface hopping and shows that there is still need for simple, robust, and generally applicable correction schemes.

History

Email Address of Submitting Author

f.plasser@lboro.ac.uk

Institution

Loughborough University

Country

United Kingdom

ORCID For Submitting Author

0000-0003-0751-148X

Declaration of Conflict of Interest

No conflict of interest.

Version Notes

Preprint version, before initial submission.

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