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

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..., , # Using density-corrected DFT to understand density-driven and functional-dependent errors in ab initio simulations of the hydrated electron Dataset DOI: [10.5061/dryad.80gb5mm32](https://doi.org/10.5061/dryad.80gb5mm32) ## Data set Overview The Folders in this repository contain many sample inputs using various density functional approximations (DFAs) to investigate charge delocalization of both the Kevan water structure and our first-shell snapshots of our hydrated electron trajectories for both the combined system made up of waters, a ghost atom, and a sulfur atom and subsystems where charge delocalization is studied with sulfur plus the ghost atom and waters plus the ghost atom giving two separate calculations. The trajectories were obtained using the CP2K package and charge delocalization calculations were conducted with QCHEM software package. The following files helped elucidate our aim to determine whether applying DC-DFT reduces density-driven errors and if this improves the..., ,水合电子（hydrated electron）是液态水中的过剩电子，在众多化学过程中发挥关键作用，这促使学界开展了大量研究工作，以表征其在溶液中的结构、动力学与反应活性。近年来，用于理解这一引人关注的化学物种的理论方法多采用基于密度泛函理论（density functional theory, DFT）的从头算（ab initio）模拟。尽管从头算DFT方法可用于研究水合电子的反应活性，但该方法存在显著的自相互作用误差（self-interaction error, SIE）。密度校正DFT（density-corrected DFT, DC-DFT）提供了缓解SIE的框架：该方法通过将给定密度泛函对应的自洽密度替换为哈特利-福克（Hartree-Fock, HF）密度，以最小化密度驱动的误差。本研究探究了密度校正对DFT模拟水合电子的计算性质的影响。首先，我们针对由模型八面体水合电子水团簇构成的体系分析了电荷离域现象。本研究主题为「基于密度校正DFT探究水合电子从头算模拟中的密度驱动误差与泛函依赖误差」。 数据集DOI：[10.5061/dryad.80gb5mm32](https://doi.org/10.5061/dryad.80gb5mm32) ## 数据集概述 本仓库中的文件夹包含多组示例输入文件，采用多种密度泛函近似（density functional approximations, DFAs），用于探究凯万水结构（Kevan water structure）与我们的水合电子轨迹第一壳层快照的电荷离域特性。研究体系分为两类：一类为由水分子、幽灵原子（ghost atom）与硫原子共同组成的复合体系；另一类为子体系，分别通过「硫+幽灵原子」和「水分子+幽灵原子」开展两组独立计算以研究电荷离域。轨迹数据通过CP2K软件包获取，电荷离域计算则使用QCHEM软件包完成。本研究旨在验证施加DC-DFT是否能够降低密度驱动的误差，并改善相关模拟效果（原文此处存在省略）。