Elastic scattering of electrons by water: an ab initio study

TL;DR

This paper introduces a new ab initio computational method for accurately modeling elastic electron scattering by water molecules and clusters, capturing complex multi-scattering and correlation effects often neglected in traditional approaches.

Contribution

The authors develop a novel theoretical framework that solves the Lippmann-Schwinger equation for non-spherical potentials, enabling precise calculations of continuum states for molecular systems.

Findings

Achieved good agreement with experimental elastic scattering data for water.

Extended the method to model electron scattering on water clusters and Zundel cation.

Demonstrated potential to include inelastic scattering and heavy particles.

Abstract

In this work we devise a theoretical and computational method to compute the elastic scattering of electrons from a non-spherical potential, such as in the case of molecules and molecular aggregates. Its main feature is represented by the ability of calculating accurate wave functions for continuum states of polycentric systems via the solution of the Lippmann-Schwinger equation, including both the correlation effects and multi-scattering interference terms, typically neglected in widely used approaches, such as the Mott theory. Within this framework, we calculate the purely elastic scattering matrix elements. As a test case, we apply our scheme to the modelling of electron-water elastic scattering. The Dirac-Hartree-Fock self-consistent field method is used to determine the non-spherical molecular potential projected on a functional space spanned by Gaussian basis set. By adding a number of multi-centric radially-arranged $s$-type Gaussian functions, whose exponents are system-dependent and optimized to reproduce the properties of the continuum electron wave function in different energy regions, we are able to achieve unprecedented access to the description of the low energy range of the spectrum ($0.001< E < 10$ eV) up to keV, finding a good agreement with experimental data and previous theoretical results. To show the potential of our approach, we also compute the total elastic scattering cross section of electrons impinging on clusters of water molecules and zundel cation. Our method can be extended to deal with inelastic scattering events and heavy-charged particles.