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# Partial Molar Solvation Volume of the Hydrated Electron Simulated Via DFT

journal contribution

posted on 2024-02-29, 18:37 authored by William
R. Borrelli, Kenneth J. Mei, Sanghyun J. Park, Benjamin J. SchwartzDifferent simulation models of the hydrated electron
produce different
solvation structures, but it has been challenging to determine which
simulated solvation structure, if any, is the most comparable to experiment.
In a recent
work, Neupane et al. [

*J. Phys. Chem. B***2023**, 127, 5941–5947] showed using Kirkwood–Buff theory that the partial molar volume of the hydrated electron, which is known experimentally, can be readily computed from an integral over the simulated electron–water radial distribution function. This provides a sensitive way to directly compare the hydration structure of different simulation models of the hydrated electron with experiment. Here, we compute the partial molar volume of an ab-initio-simulated hydrated electron model based on density-functional theory (DFT) with a hybrid functional at different simulated system sizes. We find that the partial molar volume of the DFT-simulated hydrated electron is not converged with respect to the system size for simulations with up to 128 waters. We show that even at the largest simulation sizes, the partial molar volume of DFT-simulated hydrated electrons is underestimated by a factor of 2 with respect to experiment, and at the standard 64-water size commonly used in the literature, DFT-based simulations underestimate the experimental solvation volume by a factor of ∼3.5. An extrapolation to larger box sizes does predict the experimental partial molar volume correctly; however, larger system sizes than those explored here are currently intractable without the use of machine-learned potentials. These results bring into question what aspects of the predicted hydrated electron radial distribution function, as calculated by DFT-based simulations with the PBEh-D3 functional, deviate from the true solvation structure.## History

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## Keywords

partial molar volumeneupane et allargest simulation sizeslarger box sizesexperimental solvation volumedifferent simulation modelscurrently intractable without5941 – 5947true solvation structuresimulated solvation structuresimulated hydrated electronslarger system sizessimulated hydrated electronbased simulations underestimatehydrated electronhydration structuresystem sizebased simulations∼ 3standard 64sensitive wayresults bringrecent workreadily computedlearned potentialsknown experimentallyhybrid functionalfunctional theorydirectly compared3 functional128 waters

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