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Title: The ionization potential of aqueous hydroxide computed using many-body perturbation theory

Abstract

The ionization potentials of electrolyte solutions provide important information about the electronic structure of liquids and solute-solvent interactions. We analyzed the positions of solute and solvent bands of aqueous hydroxide and the influence of the solvent environment on the ionization potential of hydroxide ions. We used the concept of a computational hydrogen electrode to define absolute band positions with respect to vacuum. We found that many-body perturbation theory in the G{sub 0} W{sub 0} approximation substantially improves the relative and absolute positions of the band edges of solute and solvent with respect to those obtained within Density Functional Theory, using semi-local functionals, yielding results in satisfactory agreement with recent experiments.

Authors:
;  [1];  [2];  [3];  [4]
  1. Department of Chemistry, University of Cambridge, Cambridge CB2 1EW (United Kingdom)
  2. Department of Chemistry, University of California, Davis, California 95616 (United States)
  3. (United States)
  4. The Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States)
Publication Date:
OSTI Identifier:
22419894
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 3; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY FUNCTIONAL METHOD; ELECTRONIC STRUCTURE; HYDROXIDES; INTERACTIONS; LIQUIDS; SOLUTES; SOLUTIONS; SOLVENTS

Citation Formats

Opalka, Daniel, E-mail: do293@cam.ac.uk, Sprik, Michiel, Pham, Tuan Anh, Lawrence Livermore National Laboratory, Livermore, California 94551, and Galli, Giulia. The ionization potential of aqueous hydroxide computed using many-body perturbation theory. United States: N. p., 2014. Web. doi:10.1063/1.4887259.
Opalka, Daniel, E-mail: do293@cam.ac.uk, Sprik, Michiel, Pham, Tuan Anh, Lawrence Livermore National Laboratory, Livermore, California 94551, & Galli, Giulia. The ionization potential of aqueous hydroxide computed using many-body perturbation theory. United States. doi:10.1063/1.4887259.
Opalka, Daniel, E-mail: do293@cam.ac.uk, Sprik, Michiel, Pham, Tuan Anh, Lawrence Livermore National Laboratory, Livermore, California 94551, and Galli, Giulia. Mon . "The ionization potential of aqueous hydroxide computed using many-body perturbation theory". United States. doi:10.1063/1.4887259.
@article{osti_22419894,
title = {The ionization potential of aqueous hydroxide computed using many-body perturbation theory},
author = {Opalka, Daniel, E-mail: do293@cam.ac.uk and Sprik, Michiel and Pham, Tuan Anh and Lawrence Livermore National Laboratory, Livermore, California 94551 and Galli, Giulia},
abstractNote = {The ionization potentials of electrolyte solutions provide important information about the electronic structure of liquids and solute-solvent interactions. We analyzed the positions of solute and solvent bands of aqueous hydroxide and the influence of the solvent environment on the ionization potential of hydroxide ions. We used the concept of a computational hydrogen electrode to define absolute band positions with respect to vacuum. We found that many-body perturbation theory in the G{sub 0} W{sub 0} approximation substantially improves the relative and absolute positions of the band edges of solute and solvent with respect to those obtained within Density Functional Theory, using semi-local functionals, yielding results in satisfactory agreement with recent experiments.},
doi = {10.1063/1.4887259},
journal = {Journal of Chemical Physics},
number = 3,
volume = 141,
place = {United States},
year = {Mon Jul 21 00:00:00 EDT 2014},
month = {Mon Jul 21 00:00:00 EDT 2014}
}