Statistical simulations of photoelectron spectral functions for aqueous solutions.

A previously devised statistical model for the evaluation of solvation shifts of electron binding energies is generalized to photoelectron spectral functions. Solvation shifts, widths, and deviations from normality are given by the first, second, and third moments of the energy distribution, respectively. The total-energy distribution as well as the Coulomb and polarization contributions are explicitly calculated by Monte Carlo simulations, thereby obtaining the full band shape. Applications are performed for liquid water and sodium ions at infinite aqueous solution.