Assessing the performance of coupled-trajectory schemes on full-dimensional two-state linear vibronic coupling models
Abstract
We investigate the performance of coupled-trajectory methods for nonadiabatic molecular dynamics in simulating the photodynamics of 4-(dimethylamino)benzonitrile (DMABN) and fulvene, with electronic structure provided by linear vibrational coupling models. We focus on the coupled-trajectory mixed quantum-classical (CTMQC) algorithm and on the (combined) coupled-trajectory Tully surface hopping [(C)CTTSH] in comparison to independent-trajectory approaches, such as multi-trajectory Ehrenfest and Tully surface hopping. Our analysis includes not only electronic populations but also additional electronic and nuclear properties in position and momentum space. For both DMABN and fulvene, the recently developed CCTTSH algorithm successfully resolves the internal inconsistencies of coupled-trajectory Tully surface hopping. Instead, we find that DMABN highlights a significant weakness of CTMQC, which arises when the trajectories remain for a long time in the vicinity of a region of strong nonadiabaticity.
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BibTeX
@article{schurger2026assessing,
title = {{Assessing the performance of coupled-trajectory schemes on full-dimensional two-state linear vibronic coupling models}},
author = {Peter Schürger and Lea Ibele and David Lauvergnat and Federica Agostini},
journal = {The Journal of Chemical Physics},
year = {2026},
month = sep,
doi = {10.1063/5.0252505},
url = {https://hal.science/hal-05737523v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Assessing the performance of coupled-trajectory schemes on full-dimensional two-state linear vibronic coupling models
AU - Peter Schürger
AU - Lea Ibele
AU - David Lauvergnat
AU - Federica Agostini
PY - 2026
DA - 2026/09/03
JO - The Journal of Chemical Physics
DO - 10.1063/5.0252505
UR - https://hal.science/hal-05737523v1
AB - We investigate the performance of coupled-trajectory methods for nonadiabatic molecular dynamics in simulating the photodynamics of 4-(dimethylamino)benzonitrile (DMABN) and fulvene, with electronic structure provided by linear vibrational coupling models. We focus on the coupled-trajectory mixed quantum-classical (CTMQC) algorithm and on the (combined) coupled-trajectory Tully surface hopping [(C)CTTSH] in comparison to independent-trajectory approaches, such as multi-trajectory Ehrenfest and Tully surface hopping. Our analysis includes not only electronic populations but also additional electronic and nuclear properties in position and momentum space. For both DMABN and fulvene, the recently developed CCTTSH algorithm successfully resolves the internal inconsistencies of coupled-trajectory Tully surface hopping. Instead, we find that DMABN highlights a significant weakness of CTMQC, which arises when the trajectories remain for a long time in the vicinity of a region of strong nonadiabaticity.
SN - 0021-9606
SN - 1089-7690
ER -