Combining the Maximum Overlap Method with Multiwavelets for Core-Ionisation Energy Calculations

Abstract

We present a protocol for computing core-ionisation energies for molecules, which is essential for reproducing X-Ray photoelectron spectroscopy experiments. The electronic structure of both the ground state and the core-ionised states are computed using Multiwavelets and Density-Functional Theory, where the core ionisation energies are computed by virtue of the $Δ$SCF method. To avoid the collapse of the core-hole state or its delocalisation, we make use of the Maximum Overlap Method, which provides a constraint on the orbital occupation. Combining Multiwavelets with the Maximum Overlap Method allows for the first time an all-electron calculation of core-ionisation energies with Multiwavelets, avoiding known issues connected to the use of Atomic Orbitals (slow convergence with respect to the basis set limit, numerical instabilities of core-hole states for large systems). We show that our results are consistent with previous Multiwavelet calculations which made use of pseudopotentials, and are generally more precise than corresponding Atomic Orbital calculations. We analyse the results in terms of precision compared to both Atomic Orbital calculations and Multiwavelets+pseudopotentials calculations. Moreover, we demonstrate how the protocol can be applied to target molecules of relatively large size. Both closed-shell and open-shell methods have been implemented.