Accurate prediction of K-edge excitation energies using state-specific self-consistent perturbation theory

TL;DR

This paper introduces an OBMP2-based self-consistent perturbation method for accurately predicting K-edge excitation energies, outperforming traditional techniques and improving convergence for open-shell and bond-stretching systems.

Contribution

The paper develops and applies an OBMP2-based approach for K-edge excitation energies, demonstrating superior accuracy and robustness over existing methods.

Findings

OBMP2-based method outperforms ΔDFT, EOM-CCSD, and USTEOM-CCSD.

The approach improves convergence issues in open-shell systems.

It provides a robust and accurate alternative for K-edge excited state calculations.

Abstract

We present the application of the recently developed one-body M{\o}ller--Plesset perturbation theory (OBMP2) to the prediction of K-edge excited states. OBMP2 is a self-consistent perturbation theory in which a canonical transformation followed by a cumulant approximation yields an effective one-body Hamiltonian. This resulting operator augments the standard Fock operator with a one-body correlation potential containing double-excitation MP2 amplitudes, allowing molecular orbitals and orbital energies to be optimized in the presence of correlation. This self-consistent framework mitigates convergence and accuracy issues often encountered in standard non-iterative MP2 for open-shell systems and bond-stretching regimes. In this work, we evaluate the performance of an OBMP2-based approach for the calculation of K-edge excitations. Utilizing benchmark test sets of both closed-shell and open-shell molecules, we demonstrate that our method outperforms established standard techniques, including $\Delta$DFT, EOM-CCSD, and USTEOM-CCSD. Our findings establish the OBMP2-based $\Delta$SCF protocol as a robust and accurate new computational method for the treatment of K-edge excited states.