Which Physical Phenomena Determine the Ionization Potential of Liquid Water?
Which Physical Phenomena Determine the Ionization Potential of Liquid Water?
复制标题
哪些物理现象决定液态水的电离势？
DOI：
10.1021/acs.jpcb.2c07639
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Pavanello, Michele
中科院分区：
文献类型：
--
作者：
Martinez B, Jessica A.;Paetow, Lukas;Tölle, Johannes;Shao, Xuecheng;Ramos, Pablo;Neugebauer, Johannes;Pavanello, Michele
从各个分子的相应属性来理解和预测分子液体的属性是非常困难的，因为液体中的分子之间存在协作行为。这对于水来说尤其重要，因为与气相相比，即使是最基本的分子特性（例如偶极矩）在液体中也有根本不同。在这项工作中，我们通过剖析构成液体的各个分子的单独贡献来关注液态水的电离势（IP）。这是通过使用周期性子系统 DFT 来实现的，这是一种基于密度嵌入的最先进的电子结构方法。我们确定并评估了电子对水 IP 的四个重要贡献：（1）平均场，在 Hartree-Fock 水平上评估； (2) 电子关联，通过 DFT 和基于波函数的方法合并； (3) 与环境的相互作用和 (4) 环境的极化，两者都是通过密度嵌入从头开始评估的。此外，我们分析了它们相对于液态水结构波动对IP的影响，揭示了意想不到的隐藏相关性，证实光电子光谱的展宽主要是由限制在第一溶剂化壳层中的分子间相互作用引起的。
Understanding and predicting the properties of molecular liquids from the corresponding properties of the individual molecules is notoriously difficult because there is cooperative behavior among the molecules in the liquid. This is particularly relevant for water, where even the most fundamental molecular properties, such as the dipole moment, are radically different in the liquid compared to the gas phase. In this work, we focus on the ionization potential (IP) of liquid water by dissecting its individual contributions from the individual molecules making up the liquid. This is achieved by using periodic subsystem DFT, a state-of-the-art electronic structure method based on density embedding. We identify and evaluate four important electronic contributions to the IP of water: (1) mean-field, evaluated at the Hartree–Fock level; (2) electronic correlation, incorporated via DFT and wave function-based methods; (3) interaction with and (4) polarization of the environment, both evaluated ab initio with density embedding. Furthermore, we analyze their impact on the IP relative to the structural fluctuation of liquid water, revealing unexpected, hidden correlations, confirming that the broadening of the photoelectron spectra is mostly caused by intermolecular interactions confined in the first solvation shell.