期刊
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
卷 119, 期 1, 页码 -出版社
WILEY
DOI: 10.1002/qua.25801
关键词
DFT; embedding; periodic boundary conditions; water
类别
资金
- US Department of Energy [DE-SC0018343]
- Ministry of Higher Education and Research, Hauts de France council
- European Regional Development Fund
- French National Research Agency [ANR-11-LABX-0005-01]
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-SC0018343]
- Hauts de France council
- U.S. Department of Energy (DOE) [DE-SC0018343] Funding Source: U.S. Department of Energy (DOE)
Calculations of charged systems in periodic boundary conditions (PBC) are problematic because there are spurious interactions between the charges in different periodic images that can affect the physical picture. In addition, the intuitive limit of Coulomb interactions decaying to zero as the interacting charges are placed at infinite separation no longer applies, and for example total energies become undefined. Leveraging subsystem density functional theory (also known as density embedding) we define an impurity model that embeds a finite neutral or charged subsystem within an extended (infinite) surrounding subsystem. The combination of the impurity model and a consistent choice of the Coulomb reference provides us with an algorithm for evaluating the ionization potential (IP) in extended systems. We demonstrate our approach in a pilot calculation of the IP of liquid water, based on a configuration from a prior ab initio molecular dynamics (AIMD) simulation of liquid water (Genova et al., J. Chem. Phys. 2016, 144, 234105). The calculations with the impurity model capture the broadening on the ionization energies introduced by the interactions between the water molecules. Furthermore, the calculated average IP value (10.5 eV) compare favorably to experiments (9.9-10.06 eV) and very recent simulations based on the GW approximation (10.55 eV), while at the same time outperforming density embedding calculations carried out with a naive handling of the electrostatic interactions (about 7 eV).
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据