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Using density-corrected DFT to understand density-driven and functional-dependent errors in ab initio simulations of the hydrated electron

Borrelli, William R.1; Guardado Sandoval, José L.1; Schwartz, Benjamin J.1

Research facility: University of California, Los Angeles
Published Apr 20, 2026 on Dryad. https://doi.org/10.5061/dryad.80gb5mm32

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Abstract

The hydrated electron, an excess electron in liquid water, plays a crucial role in a plethora of chemical processes, motivating extensive research efforts to characterize its structure, dynamics, and reactivity in solution. Recent theoretical approaches for understanding this intriguing object have involved ab initio simulations based on density functional theory (DFT). Although ab initio DFT methods allow for the study of hydrated electron reactivity, they also suffer from significant self-interaction error (SIE). Density-corrected DFT (DC-DFT) provides a framework to mitigate SIE; the method minimizes density-driven errors by replacing the self-consistent density associated with a given density functional with the Hartree-Fock (HF) density. Here, we investigate how the use of density correction affects the calculated properties of DFT-simulated hydrated electrons. First, we analyzed charge delocalization in a system consisting of a model octahedral hydrated electron water cluster (the so-called Kevan structure) along with a spatially separated sulfur atom. We show that the use of density correction indeed reduces SIE in comparison to a standard DFT global hybrid functional. We then propagate molecular dynamics trajectories of the hydrated electron using DC-DFT, where we find that DC further localizes electron density in the cavity region, a signature of reduced charge delocalization. Unfortunately, the decreased radiation of gyration of the spin density and corresponding tightening of the local solvation structure from density correction causes predicted observables to deviate further from experimental measurements than when density correction is not employed. This indicates that the difficulties with DFT to simulate hydrated electrons are primarily due to the inherent approximations in DFT rather than density-driven errors due to SIE.