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Main Authors: Pak, Sarah, Dada, Muhammed A., Govind, Niranjan, Nascimento, Daniel R.
Format: Preprint
Published: 2025
Subjects:
Online Access:https://arxiv.org/abs/2503.15462
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author Pak, Sarah
Dada, Muhammed A.
Govind, Niranjan
Nascimento, Daniel R.
author_facet Pak, Sarah
Dada, Muhammed A.
Govind, Niranjan
Nascimento, Daniel R.
contents Spectroscopic techniques based on core-level excitations provide powerful tools for probing molecular and electronic structures with high spatial resolution. However, accurately calculating spectral features at the L or M edges is challenging due to the significant influence of spin-orbit and multiplet effects. While scalar-relativistic effects can be incorporated at minimal computational cost, accounting for spin-orbit interactions requires more complex computational frameworks. In this work, we develop and apply the state-interaction approach, incorporating relativistic effects using the ZORA-Kohn-Sham Hamiltonian, to simulate near-edge soft X-ray absorption spectra for closed-shell transition metal complexes. The computed spin-orbit splittings closely match those obtained from more rigorous methods. This approach provides a practical and cost-effective alternative to more rigorous two-component methods, making it particularly valuable for large-scale calculations and applications such as resonant inelastic X-ray scattering simulations, where capturing a large number of excited states is essential.
format Preprint
id arxiv_https___arxiv_org_abs_2503_15462
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Fast simulation of soft x-ray near-edge spectra using a relativistic state-interaction approach: Application to closed-shell transition metal complexes
Pak, Sarah
Dada, Muhammed A.
Govind, Niranjan
Nascimento, Daniel R.
Chemical Physics
Spectroscopic techniques based on core-level excitations provide powerful tools for probing molecular and electronic structures with high spatial resolution. However, accurately calculating spectral features at the L or M edges is challenging due to the significant influence of spin-orbit and multiplet effects. While scalar-relativistic effects can be incorporated at minimal computational cost, accounting for spin-orbit interactions requires more complex computational frameworks. In this work, we develop and apply the state-interaction approach, incorporating relativistic effects using the ZORA-Kohn-Sham Hamiltonian, to simulate near-edge soft X-ray absorption spectra for closed-shell transition metal complexes. The computed spin-orbit splittings closely match those obtained from more rigorous methods. This approach provides a practical and cost-effective alternative to more rigorous two-component methods, making it particularly valuable for large-scale calculations and applications such as resonant inelastic X-ray scattering simulations, where capturing a large number of excited states is essential.
title Fast simulation of soft x-ray near-edge spectra using a relativistic state-interaction approach: Application to closed-shell transition metal complexes
topic Chemical Physics
url https://arxiv.org/abs/2503.15462