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

Fuente: arXiv
Enregistré dans:
Détails bibliographiques
Auteur principal: Tran, Lan Nguyen
Format: Preprint
Publié: 2026
Sujets:
Accès en ligne:
Tags: Ajouter un tag
Pas de tags, Soyez le premier à ajouter un tag!
_version_ 1866908881924390912
author Tran, Lan Nguyen
author_facet Tran, Lan Nguyen
contents We present the application of the recently developed one-body Møller--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 $Δ$DFT, EOM-CCSD, and USTEOM-CCSD. Our findings establish the OBMP2-based $Δ$SCF protocol as a robust and accurate new computational method for the treatment of K-edge excited states.
format Preprint
id arxiv_https___arxiv_org_abs_2603_11893
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Accurate prediction of K-edge excitation energies using state-specific self-consistent perturbation theory
Tran, Lan Nguyen
Chemical Physics
We present the application of the recently developed one-body Møller--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 $Δ$DFT, EOM-CCSD, and USTEOM-CCSD. Our findings establish the OBMP2-based $Δ$SCF protocol as a robust and accurate new computational method for the treatment of K-edge excited states.
title Accurate prediction of K-edge excitation energies using state-specific self-consistent perturbation theory
topic Chemical Physics
url https://arxiv.org/abs/2603.11893