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research article

Ehrenfest dynamics accelerated with SPEED

Scheidegger, Alan  
•
Vaníček, Jiří  
July 22, 2025
The Journal of Chemical Physics

Mixed quantum-classical methods, such as surface hopping and Ehrenfest dynamics, have proven useful for describing molecular processes involving multiple electronic states. These methods require propagating many independent trajectories, which is computationally demanding. Therefore, we propose the single potential evaluation Ehrenfest dynamics (SPEED), a variation of Ehrenfest dynamics where all trajectories are propagated using a common local quadratic effective potential in the diabatic representation. This approach replaces the computational cost of propagating multiple trajectories with the evaluation of a single Hessian at each time step. We demonstrate the equivalence of standard Ehrenfest dynamics and SPEED in two realistic systems with (at most) quadratic diabatic potential energy surfaces and vibronic couplings: a quadratic vibronic coupling Hamiltonian model describing internal conversion in pyrazine and a model of atomic adsorption on a solid surface. The efficiency gain of our approach is particularly advantageous in on-the-fly ab initio applications. For this reason, we combined SPEED with the ALMO(MSDFT2) electronic structure method, which provides the diabatic potential describing charge transfer between two molecules. We find that SPEED qualitatively captures the temperature dependence of the hole transfer rate between two furan moieties and accurately predicts the final charge distribution after the collision. In contrast, but as expected, our approach is insufficient for describing photoisomerization of retinal due to the high anharmonicity of the potential energy surfaces already in the diabatic representation.

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Type
research article
DOI
10.1063/5.0276025
Author(s)
Scheidegger, Alan  

École Polytechnique Fédérale de Lausanne

Vaníček, Jiří  

École Polytechnique Fédérale de Lausanne

Date Issued

2025-07-22

Publisher

AIP Publishing

Published in
The Journal of Chemical Physics
Volume

163

Issue

4

Article Number

044105

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
FunderFunding(s)Grant NumberGrant URL

Swiss National Science Foundation

NCCR MUST (Molecular Ultrafast Science and Technology)

Horizon 2020 Framework Program

683069-MOLEQULE

Available on Infoscience
July 25, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/252522
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