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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.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; German Research Foundation (DFG); National Science Foundation (NSF)
OSTI Identifier:
1389613
Report Number(s):
LLNL-JRNL-745805
Journal ID: ISSN 2375-2548; 135681
DOE Contract Number:  
AC52-07NA27344; 5J-30161-0010A; SE 2253/3-1; CHE-1301465; SC0008938; AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 6; Journal ID: ISSN 2375-2548
Publisher:
AAAS
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. Fri . "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},
issn = {2375-2548},
number = 6,
volume = 3,
place = {United States},
year = {2017},
month = {6}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy
journal, August 2015

  • Smith, Jacob W.; Lam, Royce K.; Shih, Orion
  • The Journal of Chemical Physics, Vol. 143, Issue 8
  • DOI: 10.1063/1.4928867

On the hydration and hydrolysis of carbon dioxide
journal, October 2011


Photoelectron Spectra of Aqueous Solutions from First Principles
journal, May 2016

  • Gaiduk, Alex P.; Govoni, Marco; Seidel, Robert
  • Journal of the American Chemical Society, Vol. 138, Issue 22
  • DOI: 10.1021/jacs.6b00225

Architecture of Qbox: A scalable first-principles molecular dynamics code
journal, January 2008

  • Gygi, F.
  • IBM Journal of Research and Development, Vol. 52, Issue 1.2
  • DOI: 10.1147/rd.521.0137

Screened hybrid density functionals applied to solids
journal, April 2006

  • Paier, J.; Marsman, M.; Hummer, K.
  • The Journal of Chemical Physics, Vol. 124, Issue 15
  • DOI: 10.1063/1.2187006

Energy band gaps and lattice parameters evaluated with the Heyd-Scuseria-Ernzerhof screened hybrid functional
journal, November 2005

  • Heyd, Jochen; Peralta, Juan E.; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 123, Issue 17
  • DOI: 10.1063/1.2085170

Crystallization design of MnO2 towards better supercapacitance
journal, January 2012

  • Zhang, Yuanjian; Sun, Congting; Lu, Pai
  • CrystEngComm, Vol. 14, Issue 18
  • DOI: 10.1039/c2ce25610j

A Universal Approach to Solvation Modeling
journal, June 2008

  • Cramer, Christopher J.; Truhlar, Donald G.
  • Accounts of Chemical Research, Vol. 41, Issue 6
  • DOI: 10.1021/ar800019z

Dye-Sensitized Solar Cells
journal, November 2010

  • Hagfeldt, Anders; Boschloo, Gerrit; Sun, Licheng
  • Chemical Reviews, Vol. 110, Issue 11
  • DOI: 10.1021/cr900356p

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Dipolar Correlations and the Dielectric Permittivity of Water
journal, June 2007


Photoemission Spectra and Density Functional Theory Calculations of 3d Transition Metal–Aqua Complexes (Ti–Cu) in Aqueous Solution
journal, June 2014

  • Yepes, Diana; Seidel, Robert; Winter, Bernd
  • The Journal of Physical Chemistry B, Vol. 118, Issue 24
  • DOI: 10.1021/jp5012389

Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights
journal, October 2015

  • Gauthier, Magali; Carney, Thomas J.; Grimaud, Alexis
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 22
  • DOI: 10.1021/acs.jpclett.5b01727

Ten-percent solar-to-fuel conversion with nonprecious materials
journal, September 2014

  • Cox, Casandra R.; Lee, Jungwoo Z.; Nocera, Daniel G.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 39
  • DOI: 10.1073/pnas.1414290111

Materials for electrochemical capacitors
journal, November 2008

  • Simon, Patrice; Gogotsi, Yury
  • Nature Materials, Vol. 7, Issue 11
  • DOI: 10.1038/nmat2297

Photoelectron emission spectroscopy of aqueous solutions
journal, February 1982


Optimally smooth norm-conserving pseudopotentials
journal, December 1985


Band Offsets at Semiconductor-Oxide Interfaces from Hybrid Density-Functional Calculations
journal, September 2008


First-Principles Theory of Quasiparticles: Calculation of Band Gaps in Semiconductors and Insulators
journal, September 1985


Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008


Calculation of Electrochemical Energy Levels in Water Using the Random Phase Approximation and a Double Hybrid Functional
journal, February 2016


Towards an assessment of the accuracy of density functional theory for first principles simulations of water. II
journal, September 2004

  • Schwegler, Eric; Grossman, Jeffrey C.; Gygi, François
  • The Journal of Chemical Physics, Vol. 121, Issue 11
  • DOI: 10.1063/1.1782074

Interfacial Effects on the Band Edges of Functionalized Si Surfaces in Liquid Water
journal, November 2014

  • Pham, Tuan Anh; Lee, Donghwa; Schwegler, Eric
  • Journal of the American Chemical Society, Vol. 136, Issue 49
  • DOI: 10.1021/ja5079865

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals
journal, December 2015

  • Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo
  • The Journal of Chemical Physics, Vol. 143, Issue 24
  • DOI: 10.1063/1.4938189

Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries
journal, October 2004


In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+
journal, August 2008


Electrochemical Windows of Room-Temperature Ionic Liquids from Molecular Dynamics and Density Functional Theory Calculations
journal, June 2011

  • Ong, Shyue Ping; Andreussi, Oliviero; Wu, Yabi
  • Chemistry of Materials, Vol. 23, Issue 11
  • DOI: 10.1021/cm200679y

Photoemission from Liquid Aqueous Solutions
journal, April 2006

  • Winter, Bernd; Faubel, Manfred
  • Chemical Reviews, Vol. 106, Issue 4
  • DOI: 10.1021/cr040381p

Aqueous Redox Chemistry and the Electronic Band Structure of Liquid Water
journal, November 2012

  • Adriaanse, Christopher; Cheng, Jun; Chau, Vincent
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 23
  • DOI: 10.1021/jz3015293

Methods of photoelectrode characterization with high spatial and temporal resolution
journal, January 2015

  • Esposito, Daniel V.; Baxter, Jason B.; John, Jimmy
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE00835B

Quantum Mechanical Continuum Solvation Models
journal, August 2005

  • Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto
  • Chemical Reviews, Vol. 105, Issue 8
  • DOI: 10.1021/cr9904009

Photoelectron spectroscopy of aqueous solutions: Streaming potentials of NaX (X = Cl, Br, and I) solutions and electron binding energies of liquid water and X
journal, May 2014

  • Kurahashi, Naoya; Karashima, Shutaro; Tang, Ying
  • The Journal of Chemical Physics, Vol. 140, Issue 17
  • DOI: 10.1063/1.4871877

Aqueous Transition-Metal Cations as Impurities in a Wide Gap Oxide: The Cu 2+ /Cu + and Ag 2+ /Ag + Redox Couples Revisited
journal, August 2014

  • Liu, Xiandong; Cheng, Jun; Sprik, Michiel
  • The Journal of Physical Chemistry B, Vol. 119, Issue 3
  • DOI: 10.1021/jp506691h

Probing the electronic structure of liquid water with many-body perturbation theory
journal, February 2014


The ionization potential of aqueous hydroxide computed using many-body perturbation theory
journal, July 2014

  • Opalka, Daniel; Pham, Tuan Anh; Sprik, Michiel
  • The Journal of Chemical Physics, Vol. 141, Issue 3
  • DOI: 10.1063/1.4887259

Self-consistent hybrid functional for condensed systems
journal, May 2014


Modelling heterogeneous interfaces for solar water splitting
journal, January 2017

  • Pham, Tuan Anh; Ping, Yuan; Galli, Giulia
  • Nature Materials, Vol. 16, Issue 4
  • DOI: 10.1038/nmat4803

A Classical Point Charge Model Study of System Size Dependence of Oxidation and Reorganization Free Energies in Aqueous Solution
journal, January 2008

  • Ayala, Regla; Sprik, Michiel
  • The Journal of Physical Chemistry B, Vol. 112, Issue 2
  • DOI: 10.1021/jp0748516

Improving accuracy and efficiency of calculations of photoemission spectra within the many-body perturbation theory
journal, February 2012


Ionization of Imidazole in the Gas Phase, Microhydrated Environments, and in Aqueous Solution
journal, April 2008

  • Jagoda-Cwiklik, Barbara; Slavíček, Petr; Cwiklik, Lukasz
  • The Journal of Physical Chemistry A, Vol. 112, Issue 16
  • DOI: 10.1021/jp711476g

Electronic Energy Levels and Band Alignment for Aqueous Phenol and Phenolate from First Principles
journal, July 2015

  • Opalka, Daniel; Pham, Tuan Anh; Sprik, Michiel
  • The Journal of Physical Chemistry B, Vol. 119, Issue 30
  • DOI: 10.1021/acs.jpcb.5b04189

Full Valence Band Photoemission from Liquid Water Using EUV Synchrotron Radiation
journal, April 2004

  • Winter, B.; Weber, R.; Widdra, W.
  • The Journal of Physical Chemistry A, Vol. 108, Issue 14
  • DOI: 10.1021/jp030263q

Highly efficient photoelectrochemical water splitting using a thin film photoanode of BiVO4/SnO2/WO3 multi-composite in a carbonate electrolyte
journal, January 2012

  • Saito, Rie; Miseki, Yugo; Sayama, Kazuhiro
  • Chemical Communications, Vol. 48, Issue 32
  • DOI: 10.1039/c2cc30713h

Will Solar-Driven Water-Splitting Devices See the Light of Day?
journal, September 2013

  • McKone, James R.; Lewis, Nathan S.; Gray, Harry B.
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm4021518

Photoelectrochemical cells for solar hydrogen production: current state of promising photoelectrodes, methods to improve their properties, and outlook
journal, January 2013

  • Li, Zhaosheng; Luo, Wenjun; Zhang, Minglong
  • Energy Environ. Sci., Vol. 6, Issue 2
  • DOI: 10.1039/C2EE22618A

Redox Potentials and Acidity Constants from Density Functional Theory Based Molecular Dynamics
journal, October 2014

  • Cheng, Jun; Liu, Xiandong; VandeVondele, Joost
  • Accounts of Chemical Research, Vol. 47, Issue 12
  • DOI: 10.1021/ar500268y

First-principles calculations for point defects in solids
journal, March 2014

  • Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
  • Reviews of Modern Physics, Vol. 86, Issue 1
  • DOI: 10.1103/RevModPhys.86.253

Transforming Anion Instability into Stability: Contrasting Photoionization of Three Protonation Forms of the Phosphate Ion upon Moving into Water
journal, October 2012

  • Pluhařová, Eva; Ončák, Milan; Seidel, Robert
  • The Journal of Physical Chemistry B, Vol. 116, Issue 44
  • DOI: 10.1021/jp306348b

First-Principle Protocol for Calculating Ionization Energies and Redox Potentials of Solvated Molecules and Ions: Theory and Application to Aqueous Phenol and Phenolate
journal, May 2012

  • Ghosh, Debashree; Roy, Anirban; Seidel, Robert
  • The Journal of Physical Chemistry B, Vol. 116, Issue 24
  • DOI: 10.1021/jp301925k

Nonempirical range-separated hybrid functionals for solids and molecules
journal, June 2016


Towards an assessment of the accuracy of density functional theory for first principles simulations of water
journal, January 2004

  • Grossman, Jeffrey C.; Schwegler, Eric; Draeger, Erik W.
  • The Journal of Chemical Physics, Vol. 120, Issue 1
  • DOI: 10.1063/1.1630560

Defect Energy Levels in Density Functional Calculations: Alignment and Band Gap Problem
journal, July 2008


Finite-size supercell correction schemes for charged defect calculations
journal, July 2012


Liquid microjet for photoelectron spectroscopy
journal, March 2009

  • Winter, Bernd
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 601, Issue 1-2
  • DOI: 10.1016/j.nima.2008.12.108

A review of electrolyte materials and compositions for electrochemical supercapacitors
journal, January 2015

  • Zhong, Cheng; Deng, Yida; Hu, Wenbin
  • Chemical Society Reviews, Vol. 44, Issue 21
  • DOI: 10.1039/C5CS00303B

A Solvent-Free, SeCN - /(SeCN) 3 - Based Ionic Liquid Electrolyte for High-Efficiency Dye-Sensitized Nanocrystalline Solar Cells
journal, June 2004

  • Wang, Peng; Zakeeruddin, Shaik M.; Moser, Jacques-E.
  • Journal of the American Chemical Society, Vol. 126, Issue 23
  • DOI: 10.1021/ja048472r

Oxidation Half-Reaction of Aqueous Nucleosides and Nucleotides via Photoelectron Spectroscopy Augmented by ab Initio Calculations
journal, December 2014

  • Schroeder, Christi A.; Pluhařová, Eva; Seidel, Robert
  • Journal of the American Chemical Society, Vol. 137, Issue 1
  • DOI: 10.1021/ja508149e

Optimization algorithm for the generation of ONCV pseudopotentials
journal, November 2015


G W calculations using the spectral decomposition of the dielectric matrix: Verification, validation, and comparison of methods
journal, April 2013


Electron Binding Energies of Aqueous Alkali and Halide Ions:  EUV Photoelectron Spectroscopy of Liquid Solutions and Combined Ab Initio and Molecular Dynamics Calculations
journal, May 2005

  • Winter, Bernd; Weber, Ramona; Hertel, Ingolf V.
  • Journal of the American Chemical Society, Vol. 127, Issue 19
  • DOI: 10.1021/ja042908l

Photoelectron spectroscopy of liquid water, some alcohols, and pure nonane in free micro jets
journal, June 1997

  • Faubel, Manfred; Steiner, Björn; Toennies, J. Peter
  • The Journal of Chemical Physics, Vol. 106, Issue 22
  • DOI: 10.1063/1.474034

Correspondence of defect energy levels in hybrid density functional theory and many-body perturbation theory
journal, September 2013


Large Scale GW Calculations
journal, May 2015

  • Govoni, Marco; Galli, Giulia
  • Journal of Chemical Theory and Computation, Vol. 11, Issue 6
  • DOI: 10.1021/ct500958p

Structure and dynamics of aqueous solutions from PBE-based first-principles molecular dynamics simulations
journal, October 2016

  • Pham, Tuan Anh; Ogitsu, Tadashi; Lau, Edmond Y.
  • The Journal of Chemical Physics, Vol. 145, Issue 15
  • DOI: 10.1063/1.4964865

Photoelectron Spectroscopy Meets Aqueous Solution: Studies from a Vacuum Liquid Microjet
journal, February 2011

  • Seidel, Robert; Thürmer, Stephan; Winter, Bernd
  • The Journal of Physical Chemistry Letters, Vol. 2, Issue 6
  • DOI: 10.1021/jz101636y