The accurate calculation of the band gap of liquid water by means of GW corrections applied to plane-wave density functional theory molecular dynamics simulations
- Author(s)
- Changming Fang, Wun-Fan Li, Rik S. Koster, Jiri Klimes, Alfons van Blaaderen, Marijn A. van Huis
- Abstract
Knowledge about the intrinsic electronic properties of water is imperative for understanding the behaviour of aqueous solutions that are used throughout biology, chemistry, physics, and industry. The calculation of the electronic band gap of liquids is challenging, because the most accurate ab initio approaches can be applied only to small numbers of atoms, while large numbers of atoms are required for having configurations that are representative of a liquid. Here we show that a high-accuracy value for the electronic band gap of water can be obtained by combining beyond-DFT methods and statistical time-averaging. Liquid water is simulated at 300 K using a plane-wave density functional theory molecular dynamics (PW-DFT-MD) simulation and a van der Waals density functional (optB88-vdW). After applying a self-consistent GW correction the band gap of liquid water at 300 K is calculated as 7.3 eV, in good agreement with recent experimental observations in the literature (6.9 eV). For simulations of phase transformations and chemical reactions in water or aqueous solutions whereby an accurate description of the electronic structure is required, we suggest to use these advanced GW corrections in combination with the statistical analysis of quantum mechanical MD simulations.
- Organisation(s)
- Computational Materials Physics
- External organisation(s)
- Center for Computational Materials Science, CMS, Utrecht University
- Journal
- Physical Chemistry Chemical Physics
- Volume
- 17
- Pages
- 365-375
- No. of pages
- 11
- ISSN
- 1463-9076
- DOI
- https://doi.org/10.1039/c4cp04202f
- Publication date
- 10-2014
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103025 Quantum mechanics, 103036 Theoretical physics, 103015 Condensed matter, 103009 Solid state physics
- Keywords
- ASJC Scopus subject areas
- General Physics and Astronomy, Physical and Theoretical Chemistry
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/7bb1494b-69f2-41dd-b319-82e37eb82e11