Accurate absolute core-electron binding energies of molecules, solids and surfaces from first-principles calculations

Abstract

Core-electron x-ray photoelectron spectroscopy is a powerful technique for studying the electronic structure and chemical composition of molecules, solids and surfaces. However, the interpretation of measured spectra and the assignment of peaks to atoms in specific chemical environments is often challenging. Here, we address this problem and introduce a parameter-free computational approach for calculating absolute core-electron binding energies. In particular, we demonstrate that accurate absolute binding energies can be obtained from the total energy difference of the ground state and a state with an explicit core hole when exchange and correlation effects are described by a recently developed meta-generalized gradient approximation and relativistic effects are included even for light elements. We carry out calculations for molecules, solids and surface species and find excellent agreement with available experimental measurements. For example, we find a mean absolute error of only 0.16 eV for a reference set of 103 molecular core-electron binding energies. The capability to calculate accurate absolute core-electron binding energies will enable new insights into a wide range of chemical surface processes that are studied by x-ray photoelectron spectroscopy.

References in corpus (4)

• Performance of the strongly constrained and appropriately normed density functional for solid-state materials
• 103-Compound Band Structure Benchmark of Post-SCF Spin-Orbit Coupling Treatments in Density-Functional Theory
• Core level binding energies in solids from first-principles
• Core electron binding energies of adsorbates on Cu(111) from first-principles calculations

Cited by in corpus (16)

• 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
• Accurate absolute and relative core-level binding energies from $GW$
• All-electron Gaussian-based $G_0{W}_0$ for Valence and Core Excitation Energies of Periodic Systems
• Accurate computational prediction of core-electron binding energies in carbon-based materials: A machine-learning model combining density-functional theory and $\mathbf{GW}$
• Relativistic Orbital Optimized Density Functional Theory for Accurate Core-Level Spectroscopy
• Accelerating core-level $GW$ calculations by combining the contour deformation approach with the analytic continuation of $W$
• Relativistic correction scheme for core-level binding energies from $GW$
• Computing X-ray absorption spectra from linear-response particles atop optimized holes
• Combining the $\Delta$-Self-Consistent-Field and GW Methods for Predicting Core Electron Binding Energies in Periodic Solids
• Predicting Core Electron Binding Energies in Elements of the First Transition Series Using the $\Delta$-Self-Consistent-Field Method
• Calculation of core-excited and core-ionized states using variational quantum deflation method and applications to photocatalyst modelling
• Franck-Condon Simulation of Vibrationally-Resolved X-ray Spectra for Diatomic Systems: Validation of Harmonic Approximation and Density Functional Theory
• Core-Ionized States and X-ray Photoelectron Spectra of Solids From Periodic Algebraic Diagrammatic Construction Theory
• Explicit core-hole single-particle methods for L- and M- edge X-ray absorption and electron energy-loss spectra
• Probing Disorder in 2CzPN using Core and Valence States
• Effects of Structural Variations to X-ray Absorption Spectra of g-C${}_3$N${}_4$: Insights from DFT and TDDFT Simulations