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Updated: Aug 21, 2025
Precise Electrochemical Sizing of Individual Electro-Inactive Particles
Published on: August 4, 2023
Electrochemistry from the atomic scale, in the electronically grand-canonical ensemble
Per Lindgren1, Georg Kastlunger1, Andrew A Peterson1
1School of Engineering, Brown University, Providence, Rhode Island 02912, USA.
Abstract:
The ability to simulate electrochemical reactions from first-principles has advanced significantly in recent years. Here, we discuss the atomistic interpretation of electrochemistry at three scales: from the electronic structure to elementary processes to constant-potential reactions. At each scale, we highlight the importance of the grand-canonical nature of the process and show that the grand-canonical energy is the natural thermodynamic state variable, which has the additional benefit of simplifying calculations. We show that atomic forces are the derivative of the grand-potential energy when the potential is fixed. We further examine the meaning of potential at the atomic scale and its link to the chemical potential and discuss the link between charge transfer and potential in several situations.
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