# Using grand-canonical DFT to investigate electrochemical reactions on semiconductor surfaces.

Tangui Le Bahers, Stephan N. Steinmann, Pascal Raybaud, Curutchet

Antton, Muhammad Akif Ramzan, Carine Michel

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Tangui Le Bahers, Stephan N. Steinmann, Pascal Raybaud, Curutchet Antton, Muhammad Akif Ramzan, et al.. Using grand-canonical DFT to investigate electrochemical reactions on semiconductor surfaces.. 9ièmes journées nationales des carburants solaires, Jul 2025, Strasbourg, France. hal-05512151

HAL Id: hal-05512151

https://hal.science/hal-05512151v1

Submitted on 17 Feb 2026

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Distributed under a Creative Commons CC BY 4.0 - Attribution - International License
Using grand-canonical DFT to investigate electrochemical reactions on semiconductor surfaces.

Tangui Le Bahers¹,², Stephan Steinmann¹, Pascal Raybaud³, Antton Curutchet¹, Akif Ramzan¹, Antton Curutchet¹, Carine Michel¹

¹ Laboratoire de Chimie UMR 5182, Lyon; ² Institut universitaire de France, Paris; ³ IFPEN, Solaize.

tangui.le_bahers@ens-lyon.fr

During an electrochemical reaction on an electrode, the polarization of the surface induces a surface charge. This charge affects several surface properties: structure, reactivity... In quantum chemistry, an advanced approach to simulate such effects is the grand-canonical (GC-)DFT in which the association of periodic boundary conditions and the charge compensation technic (either implicit or explicit) allows to tune smoothly the surface charge and thus the Fermi level of the simulated electrode. In other words, at the GC-DFT level, it is possible to simulate electro-chemical reactions on an electrode surface explicitly considering the effect of the electro-chemical potential. At the cross-road between development of application, this presentation introduces the principle of the GC-DFT. While this approach has been generally used with metal surfaces, a specific focus will be done on its behavior when dealing with semiconductor surfaces. We will then illustrate how the explicit inclusion of polarization in the calculations modifies our understanding of chemical reactivity in the case of water oxidation on CoOOH surface and CO₂ reduction on MoS₂ surface.[¹,²] The presentation will end by a perspective presentation for more advanced simulations of the electrolyte by QM/MM approaches developed in our group[³] and on the difficult definition of the Fermi level for outer-sphere electron transfers.[⁴]

<figure><img src="image_2.png" /><figcaption>Figure 1: Illustration of the use of GC-DFT to investigate water oxidation on CoOOH surface.</figcaption></figure>

References

[1] Curutchet, A., et al. Phys. Chem. Chem. Phys., **2020**, 22, 7031.

[2] Ramzan, M., et al. J. Phys. Chem. C, **2024**, 128, 10025.

[3] Abidi, N. et al., et al. ACS Appl. Mater. Inter. **2023**, 15, 25009.

[4] Melander, M. M. et al. Npj Comput. Mater. **2024**, 10, 5.