SURPRISES: when ab initio meets statistics in extended systems

Abstract

The surface photoelectron and inner shell electron spectroscopy (SURPRISES) program suite performs ab initio calculations of photoionization and non-radiative decay spectra in nanoclusters and solid state systems by using a space-energy similarity procedure to reproduce the band-like part of the spectra. This approach provides an extension of Fano resonant multichannel scattering theory dealing with the complexity arising from condensed matter calculations at a computational cost comparable to that of molecules. The bottleneck of electron spectroscopy ab initio calculations in condensed matter is the size of the Hilbert space where the wavefunctions are expanded and the increase in number of final decay states in comparison to that of atoms and molecules. In particular, the diagonalization of the interchannel interaction to take into account the correlation between the double ion and the escaping electron is impracticable when hole delocalization on valence bands and electronic excitations are included in the model. To overcome this problem SURPRISES uses a 'space-energy similarity' approach, which allows the spreading of the Auger probability over the bands without tuning semi-empirical parameters. Furthermore, a completely new feature in the landscape of ab initio resonant decay processes calculations is represented by including energy loss through a statistical approach. Using the calculated lineshape as electron source, a Monte Carlo routine simulates the effect of inelastic losses on the original lineshape. In this process, the computed spectrum can be directly compared with acquired experimental spectra, thus avoiding background subtraction, a procedure not free from uncertainty. The program can exploit the symmetry of the system under investigation to reduce the calculation scaling and may compute photoemission and Auger decay angular distribution patterns including energy loss for the electrons emitted in resonance-affected photoionization processes. In this paper, we present general methods, computational techniques and a number of numerical tests applied to the calculation of Si K–LL and O K–LL Auger spectra from different SiO2 nanoclusters.