Computational photoelectron spectroscopy of liquid water

ORAL

Abstract

We present an extensive computational study of the electronic properties of liquid water simulated with MB-pol potential [1]. Electronic properties were determined using density-functional and many-body perturbation theory methods. We find that the $G_0W_0$ approximation starting from wavefunctions obtained with dielectric-dependent hybrid functionals [2] provides the best agreement of computed photoelectron spectra with experiment. The inclusion of nuclear quantum effects softens the structure of water, broadens the lines in the spectra and yields narrower band gaps; the use of different methods for modeling water in the absence of quantum effects, such as density-functional approximations [3--4], has a weaker effect on the liquid electronic properties. Remarkably, the positions of the valence band maximum and conduction band minimum are rather sensitive to the presence of the air/liquid interface, underlining the importance of modeling realistic systems for comparison with experiment. \\[8pt] [1]~G.~R. Medders, V. Babin, F. Paesani, JCTC 10, 2906 (2014); [2]~J.~H. Skone, M. Govoni, G. Galli, PRB 89, 195112 (2014); [3]~T.~A. Pham, C. Zhang, E. Schwegler, G. Galli, PRB 89, 060202 (2014); [4]~A.~P. Gaiduk, M. Govoni, R. Seidel, J. Skone, B. Winter, G. Galli, JACS 138, 6912 (2016)

*This work was supported by MICCoM center funded through DOE/BES 5J-30161-0010A and by NSERC Postdoctoral Fellowship

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Authors

  • Alex P. Gaiduk

    • University of Chicago

  • Tuan Anh Pham

    • Lawrence Livermore National Laboratory

  • Marco Govoni

    • Institute for Molecular Engineering, University of Chicago; Materials Science Division, Argonne National Laboratory
    • Argonne National Laboratory and University of Chicago
    • Materials Science Division, Argonne National Laboratory and Institute for Molecular Engineering, University of Chicago and
    • University of Chicago and Argonne National Laboratory

  • Francesco Paesani

    • University of California, San Diego

  • Giulia Galli

    • Univ of Chicago and Argonne National Laboratory
    • Univ of Chicago
    • University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago; Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago and Materials Science Division, Argonne Natl Lab
    • Institute for Molecular Engineering, University of Chicago; Materials Science Division, Argonne National Laboratory
    • Institute for Molecular Engineering, University of Chicago, Chicago, IL 60637 and Materials Science Division, Argonne National Laboratory, Lemont, IL
    • Institute for Molecular Engineering, University of Chicago and Argonne Natl Lab
    • University of Chicago, Chicago, IL 60637, USA
    • The University of Chicago, Institute for Molecular Engineering and Argonne National Laboratory
    • Argonne National Laboratory and University of Chicago
    • Institute for Molecular Engineering, University of Chicago and Materials Science Division, Argonne National Laboratory
    • University of Chicago
    • The University of Chicago
    • University of Chicago and Argonne National Laboratory