Relativistic Orbital Optimized Density Functional Theory for Accurate Core-Level Spectroscopy

Abstract

Core-level spectra of 1s electrons of elements heavier than Ne show significant relativistic effects. We combine advances in orbital optimized DFT (OO-DFT) with the spin-free exact two-component (X2C) model for scalar relativistic effects, to study K-edge spectra of third period elements. OO-DFT/X2C is found to be quite accurate at predicting energies, yielding $\sim 0.5$ eV RMS error vs experiment with the modern SCAN (and related) functionals. This marks a significant improvement over the $>50$ eV deviations that are typical for the popular time-dependent DFT (TDDFT) approach. Consequently, experimental spectra are quite well reproduced by OO-DFT/X2C, sans empirical shifts for alignment. OO-DFT/X2C combines high accuracy with ground state DFT cost and is thus a promising route for computing core-level spectra of third period elements. We also explored K and L edges of 3d transition metals to identify limitations of the OO-DFT/X2C approach in modeling the spectra of heavier atoms.

References in corpus (6)

• Orbital Optimized Density Functional Theory for Electronic Excited States
• Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining sub eV Error from a Restricted Open-Shell Kohn-Sham Approach
• Variational density functional calculations of excited states via direct optimization
• Relativistic EOM-CCSD for core-excited and core-ionized state energies based on the 4-component Dirac-Coulomb(-Gaunt) Hamiltonian
• Accurate prediction of core-level spectra of radicals at density functional theory cost via square gradient minimization and recoupling of mixed configurations
• Core Excitations with Excited State Mean Field and Perturbation Theory

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