Full-Potential Multiple Scattering Theory with Space-Filling Cells for bound and continuum states

TL;DR

This paper develops a rigorous real-space Full-Potential Multiple-Scattering-Theory (FP-MST) that overcomes previous limitations, enabling accurate electronic structure calculations and x-ray spectroscopy simulations for both bound and continuum states.

Contribution

It introduces a new, efficient scheme for generating local basis functions in FP-MST that is shape-independent and simplifies the expansion, extending MST beyond the Muffin-Tin approximation.

Findings

The theory converges absolutely as the maximum angular momentum increases.

The method is applicable to electronic structure calculations and x-ray spectroscopies.

Numerical applications demonstrate the theory's effectiveness for bound and continuum states.

Abstract

We present a rigorous derivation of a real space Full-Potential Multiple-Scattering-Theory (FP-MST), valid both for continuum and bound states, that is free from the drawbacks that up to now have impaired its development, in particular the need to use cell shape functions and rectangular matrices. In this connection we give a new scheme to generate local basis functions for the truncated potential cells that is simple, fast, efficient, valid for any shape of the cell and reduces to the minimum the number of spherical harmonics in the expansion of the scattering wave function. The method also avoids the need for saturating 'internal sums' due to the re-expansion of the spherical Hankel functions around another point in space (usually another cell center). Thus this approach, provides a straightforward extension of MST in the Muffin-Tin (MT) approximation, with only one truncation parameter given by the classical relation $l_{\rm max} = kR_b$, where $k$ is the excited (or ground state) electron wave vector and $R_b$ the radius of the bounding sphere of the scattering cell. It is shown that the theory converges absolutely in the $l_{\rm max} \to \infty$ limit. As a consequence it provides a firm ground to the use of FP-MST as a viable method for electronic structure calculations and makes possible the computation of x-ray spectroscopies, notably photo-electron diffraction, absorption and anomalous scattering among others, with the ease and versatility of the corresponding MT theory. Some numerical applications of the theory are presented, both for continuum and bound states.