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

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. Here, 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.
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  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Quantum Simulations Group; Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy and Methods for Material Development
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  3. Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry
  4. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Quantum Simulations Group
Publication Date:
Report Number(s):
Journal ID: ISSN 2375-2548; 930468
Grant/Contract Number:
AC52-07NA27344; 5J-30161-0010A; SE 2253/3-1; CHE-1301465; SC0008938; AC02-06CH11357
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 3; Journal Issue: 6; Journal ID: ISSN 2375-2548
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)
Country of Publication:
United States
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; photoelectron spectroscopy; Excited states properties; Aqueous solutions; Computational Chemistry; First-principles theory
OSTI Identifier: