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Title: Electron affinity of liquid water

Abstract

Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential of the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [3]
  1. Univ. of Chicago, IL (United States). Institute for Molecular Engineering
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of Chicago, IL (United States). Institute for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Univ. of California, San Diego, CA (United States). Department of Chemistry and Biochemistry, Materials Science and Engineering, San Diego Supercomputer Center
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; Midwest Integrated Center for Computational Materials (MICCoM); Natural Sciences and Engineering Research Council of Canada (NSERC); National Science Foundation (NSF)
OSTI Identifier:
1419951
Alternate Identifier(s):
OSTI ID: 1474381
Report Number(s):
LLNL-JRNL-741446
Journal ID: ISSN 2041-1723; 141521
Grant/Contract Number:  
AC02-06CH11357; AC52-07NA27344; CHE-1453204; ACI-1053575
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Gaiduk, Alex P., Pham, Tuan Anh, Govoni, Marco, Paesani, Francesco, and Galli, Giulia. Electron affinity of liquid water. United States: N. p., 2018. Web. doi:10.1038/s41467-017-02673-z.
Gaiduk, Alex P., Pham, Tuan Anh, Govoni, Marco, Paesani, Francesco, & Galli, Giulia. Electron affinity of liquid water. United States. doi:10.1038/s41467-017-02673-z.
Gaiduk, Alex P., Pham, Tuan Anh, Govoni, Marco, Paesani, Francesco, and Galli, Giulia. Tue . "Electron affinity of liquid water". United States. doi:10.1038/s41467-017-02673-z. https://www.osti.gov/servlets/purl/1419951.
@article{osti_1419951,
title = {Electron affinity of liquid water},
author = {Gaiduk, Alex P. and Pham, Tuan Anh and Govoni, Marco and Paesani, Francesco and Galli, Giulia},
abstractNote = {Understanding redox and photochemical reactions in aqueous environments requires a precise knowledge of the ionization potential and electron affinity of liquid water. The former has been measured, but not the latter. We predict the electron affinity of liquid water and of its surface from first principles, coupling path-integral molecular dynamics with ab initio potentials, and many-body perturbation theory. Our results for the surface (0.8 eV) agree well with recent pump-probe spectroscopy measurements on amorphous ice. Those for the bulk (0.1-0.3 eV) differ from several estimates adopted in the literature, which we critically revisit. We show that the ionization potential of the bulk and surface are almost identical; instead their electron affinities differ substantially, with the conduction band edge of the surface much deeper in energy than that of the bulk. We also discuss the significant impact of nuclear quantum effects on the fundamental gap and band edges of the liquid.},
doi = {10.1038/s41467-017-02673-z},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Tue Jan 16 00:00:00 EST 2018},
month = {Tue Jan 16 00:00:00 EST 2018}
}

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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