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 G0 W0 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: Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
authors: Daniel
authors: D
authors: Opalka
authors: Department of Chemistry, University of California, Davis, California 95616, USA.
authors: Tuan Anh
authors: TA
authors: Pham
authors: Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
authors: Michiel
authors: M
authors: Sprik
authors: The Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA.
authors: Giulia
authors: G
authors: Galli
mesh_terms: D006878:Hydroxides / Q000737:chemistry*; D011789:Quantum Theory; D012996:Solutions; D012997:Solvents / Q000737:chemistry; D013816:Thermodynamics; D014867:Water / Q000737:chemistry*
chemical_list: D006878:Hydroxides; D012996:Solutions; D012997:Solvents; D014867:Water; C031356:hydroxide ion