Photoelectron Spectra of Aqueous Solutions from First Principles.
We present a combined computational and experimental study of the photoelectron spectrum of a simple aqueous solution of NaCl. Measurements were conducted on microjets, and first-principles calculations were performed using hybrid functionals and many-body perturbation theory at the G0W0 level, starting with wave functions computed in ab initio molecular dynamics simulations. We show excellent agreement between theory and experiments for the positions of both the solute and solvent excitation energies on an absolute energy scale and for peak intensities. The best comparison was obtained using wave functions obtained with dielectric-dependent self-consistent and range-separated hybrid functionals. Our computational protocol opens the way to accurate, predictive calculations of the electronic properties of electrolytes, of interest to a variety of energy problems.
Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.
Alex P
AP
Gaiduk
Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.|Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Marco
M
Govoni
Methods for Material Development, Helmholtz-Zentrum Berlin für Materialien und Energie , D-12489 Berlin, Germany.
Robert
R
Seidel
Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.
Jonathan H
JH
Skone
Methods for Material Development, Helmholtz-Zentrum Berlin für Materialien und Energie , D-12489 Berlin, Germany.
Bernd
B
Winter
Institute for Molecular Engineering, The University of Chicago , Chicago, Illinois 60637, United States.|Materials Science Division, Argonne National Laboratory , Argonne, Illinois 60439, United States.
Giulia
G
Galli