Energy level alignment at semiconductor-water interfaces from atomistic and continuum solvation models
File(s)
Published version
Accepted version
Author(s)
Blumenthal, LB
Kahk, JMK
Sundararaman, RS
Tangney, PT
Lischner, JC
Type
Journal Article
Abstract
Accurate and efficient methods for predicting the alignment between a semiconductor's electronic energy levels and electrochemical redox potentials are needed to facilitate the computational discovery of photoelectrode materials. In this paper, we present an approach that combines many-body perturbation theory within the GW method with continuum solvation models. Specifically, quasiparticle levels of the bulk photoelectrode are referenced to the outer electric potential of the electrolyte by calculating the change in electric potential across the photoelectrode–electrolyte and the electrolyte–vacuum interfaces using continuum solvation models. We use this method to compute absolute energy levels for the prototypical rutile (TiO2) photoelectrode in contact with an aqueous electrolyte and find good agreement with predictions from atomistic simulations based on molecular dynamics. Our analysis reveals qualitative and quantitative differences of the description of the interfacial charge density in atomistic and continuum solvation models and highlights the need for a consistent treatment of electrode–electrolyte and electrolyte–vacuum interfaces for the determination of accurate absolute energy levels.
Date Issued
2017-09-11
Date Acceptance
2017-09-04
Citation
RSC Advances: an international journal to further the chemical sciences, 2017, 7 (69), pp.43660-43670
ISSN
2046-2069
Publisher
Royal Society of Chemistry
Start Page
43660
End Page
43670
Journal / Book Title
RSC Advances: an international journal to further the chemical sciences
Volume
7
Issue
69
Copyright Statement
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Sponsor
The Royal Society
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (EPSRC)
Identifier
https://pubs.rsc.org/en/content/articlelanding/2017/RA/C7RA08357B
Grant Number
UF130450
EP/N005244/1
EP/R002010/1
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
DENSITY-FUNCTIONAL THEORY
INITIO MOLECULAR-DYNAMICS
LIQUID-VAPOR INTERFACE
BAND-EDGE POSITIONS
AB-INITIO
1ST PRINCIPLES
QUASI-PARTICLE
SURFACE
RUTILE
POTENTIALS
03 Chemical Sciences
Publication Status
Published
Date Publish Online
2017-09-11