General Spin-Restricted Open-Shell Configuration Interaction Approach: Application to Metal K-Edge X-ray Absorption Spectra of Ferro- and Antiferromagnetically Coupled Dimers.

In this work, we present a generalized implementation of the previously developed restricted open-shell configuration interaction singles (ROCIS) family of methods. The new method allows us to treat high-spin (HS) ferro- as well as antiferromagnetically (AF) coupled systems while retaining the total spin as a good quantum number. To achieve this important and nontrivial goal, we employ the machinery of the iterative configuration expansion (ICE) method, which is able to tackle general configuration interaction (CI) problems on the basis of spin-adapted configuration state functions (CSFs). While ICE is designed to work in restricted orbital spaces, the new general-spin ROCIS (GS-ROCIS) method is designed to be applicable to larger molecules by employing a prototyping strategy. This new method can be applied to closed-shell, high-spin open-shell, as well as antiferromagnetic reference CSFs. In addition, GS-ROCIS can be combined with the pair natural orbital (PNO) machinery in the form of the PNO-GS-ROCIS method. With this extension, one can drastically reduce the required virtual space in the vicinity of the involved core orbitals, leading to computational savings of several orders of magnitude with negligible (<1%) loss in accuracy. To demonstrate the use of the new methodology, the metal K pre-edge X-ray absorption excitation problem of an antiferromagnetically coupled copper model dimer was investigated. By first analyzing a model copper dimer, it is shown that even for the minimum core excitation problem that involves the two antiferromagnetically coupled singly occupied orbitals and one virtual orbital, the resulting GS-ROCIS and broken-symmetry configuration interaction singles (BS-CIS) spectra may differ in terms of the number, energy position, and relative intensity of the computed bands. Furthermore, the methodology was validated to perform equally well in computing the K-edge spectra of antiferromagnetic nickel oxide dimers and mixed-valence cobalt oxide trimers. Collectively, the present development represents an important methodological advance in the application of theoretical X-ray spectroscopy.