skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electronic structure of aqueous solutions: Bridging the gap between theory and experiments

Abstract

Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.

Authors:
; ; ; ; ORCiD logo;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division; USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division - Midwest Integrated Center for Computational Materials (MICCoM); German Research Foundation (DFG); Argonne National Laboratory - Argonne Leadership Computing Facility; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1389613
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Science Advances; Journal Volume: 3; Journal Issue: 6
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Pham, Tuan Anh, Govoni, Marco, Seidel, Robert, Bradforth, Stephen E., Schwegler, Eric, and Galli, Giulia. Electronic structure of aqueous solutions: Bridging the gap between theory and experiments. United States: N. p., 2017. Web. doi:10.1126/sciadv.1603210.
Pham, Tuan Anh, Govoni, Marco, Seidel, Robert, Bradforth, Stephen E., Schwegler, Eric, & Galli, Giulia. Electronic structure of aqueous solutions: Bridging the gap between theory and experiments. United States. doi:10.1126/sciadv.1603210.
Pham, Tuan Anh, Govoni, Marco, Seidel, Robert, Bradforth, Stephen E., Schwegler, Eric, and Galli, Giulia. Thu . "Electronic structure of aqueous solutions: Bridging the gap between theory and experiments". United States. doi:10.1126/sciadv.1603210.
@article{osti_1389613,
title = {Electronic structure of aqueous solutions: Bridging the gap between theory and experiments},
author = {Pham, Tuan Anh and Govoni, Marco and Seidel, Robert and Bradforth, Stephen E. and Schwegler, Eric and Galli, Giulia},
abstractNote = {Predicting the electronic properties of aqueous liquids has been a long-standing challenge for quantum mechanical methods. However, it is a crucial step in understanding and predicting the key role played by aqueous solutions and electrolytes in a wide variety of emerging energy and environmental technologies, including battery and photoelectrochemical cell design. We propose an efficient and accurate approach to predict the electronic properties of aqueous solutions, on the basis of the combination of first-principles methods and experimental validation using state-of-the-art spectroscopic measurements. We present results of the photoelectron spectra of a broad range of solvated ions, showing that first-principles molecular dynamics simulations and electronic structure calculations using dielectric hybrid functionals provide a quantitative description of the electronic properties of the solvent and solutes, including excitation energies. The proposed computational framework is general and applicable to other liquids, thereby offering great promise in understanding and engineering solutions and liquid electrolytes for a variety of important energy technologies.},
doi = {10.1126/sciadv.1603210},
journal = {Science Advances},
number = 6,
volume = 3,
place = {United States},
year = {Thu Jun 01 00:00:00 EDT 2017},
month = {Thu Jun 01 00:00:00 EDT 2017}
}