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

Autor(en)

Changming Fang, Wun-Fan Li, Rik S. Koster, Jiri Klimes, Alfons van Blaaderen, Marijn A. van Huis

Abstrakt

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(en)

Computergestützte Materialphysik

Externe Organisation(en)

Center for Computational Materials Science, CMS, Utrecht University

Journal

Physical Chemistry Chemical Physics

Band

17

Seiten

365-375

Anzahl der Seiten

11

ISSN

1463-9076

DOI

https://doi.org/10.1039/c4cp04202f

Publikationsdatum

10-2014

Peer-reviewed

Ja

ÖFOS 2012

103025 Quantenmechanik, 103036 Theoretische Physik, 103015 Kondensierte Materie, 103009 Festkörperphysik

Schlagwörter

ASJC Scopus Sachgebiete

Allgemeine Physik und Astronomie, Physical and Theoretical Chemistry

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/7bb1494b-69f2-41dd-b319-82e37eb82e11