Cluster Perturbation Theory for Core Excited States and Core Ionization Potentials Using Core-Valence Separation.

Abstract

The development of accurate and fast computational procedures for the ab initio calculation of X-ray spectroscopies is paramount to facilitate theoretical analysis of modern X-ray experiments on molecules. Herein, we present the extension of Cluster Perturbation theory to comprehend the calculation of core excited states and core ionization potentials using the core-valence separation approximation, which has seen widespread success for various quantum chemistry methods. We derive the theoretical framework for introducing core-valence separation into Cluster Perturbation series for excitation energies and display the performance of the methodology in S(D) orbital excitation spaces. The obtained core excitation energies on a test set of medium sized organic molecules show that carbon, nitrogen, and oxygen K-edge excitation energies can be determined with errors below 2 eV relative to the CCSD reference results using the developed CPS(D) excitation energy models which can be used for systems way beyond the reach of conventional CCSD.