Modeling interfacial electron transfer using path integral molecular dynamics
Name
064119_1_5.0307179.pdf
Description
Published version
Size
5.39 MB
Format
Adobe PDF
Checksum (MD5)
e5c810c5949451349ccf353dc367c2c2
Author(s)
Park, Yoonjae
Willard, Adam P
Date Issued
February 12, 2026
Journal
The Journal of Chemical Physics
Publisher
AIP Publishing
Citation
Yoonjae Park, Adam P. Willard; Modeling interfacial electron transfer using path integral molecular dynamics. J. Chem. Phys. 14 February 2026; 164 (6): 064119.
Version
Final published version
Abstract
Outer sphere electron transfer rates can be calculated from simulation data by sampling the equilibrium statistics of the vertical energy gap. For this calculation, electron transfer is typically represented as an instantaneous change in the atomic partial charges. In this paper, we present an implementation of this procedure that utilizes an explicit path-integral representation of the transferring electron. We demonstrate our methodology by combining path integral molecular dynamics and Marcus–Hush–Chidsey theory to calculate the rate of electron transfer from a ferrocyanide complex to a constant potential gold electrode. We consider the dependence of this rate on electron transfer distance and applied potential. We find that when the electron is represented explicitly via path integral molecular dynamics, as opposed to implicitly via fixed atomic partial charges, the rates and thermodynamics are more consistent with experimental findings. We then apply our methodology to explore the role of bridging spectator cations in modifying electron transfer rates. We find, once again, that the path integral approach produces specific cation effects that are more consistent with experiment than those in which the transferring electron is represented implicitly.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1063/5.0307179
