Understanding Electron Transfer Reactions Using Constrained Density Functional Theory: Complications Due to Surface Interactions

Arsalan Hashemi, Pekka Peljo, Kari Laasonen*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

2 Citations (Scopus)
121 Downloads (Pure)


The kinetic rates of electrochemical reactions depend on electrodes and molecules in question. In a flow battery, where the electrolyte molecules are charged and discharged on the electrodes, the efficiency of the electron transfer is of crucial importance for the performance of the device. The purpose of this work is to present a systematic atomic-level computational protocol for studying electron transfer between electrolyte and electrode. The computations are done by using constrained density functional theory (CDFT) to ensure that the electron is either on the electrode or in the electrolyte. The ab initio molecular dynamics (AIMD) is used to simulate the movement of the atoms. We use the Marcus theory to predict electron transfer rates and the combined CDFT-AIMD approach to compute the parameters for the Marcus theory where it is needed. We model the electrode with a single layer of graphene and methylviologen, 4,4′-dimethyldiquat, desalted basic red 5, 2-hydroxy-1,4-naphthaquinone, and 1,1-di(2-ethanol)-4,4-bipyridinium were selected for the electrolyte molecules. All of these molecules undergo consecutive electrochemical reactions with one electron being transferred at each stage. Because of significant electrode-molecule interactions, it is not possible to evaluate outer-sphere ET. This theoretical study contributes toward the development of a realistic-level prediction of electron transfer kinetics suitable for energy storage applications.

Original languageEnglish
Pages (from-to)3398–3407
Number of pages10
JournalJournal of Physical Chemistry C
Issue number7
Early online date9 Feb 2023
Publication statusPublished - 23 Feb 2023
MoE publication typeA1 Journal article-refereed


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