Electron-Affinity Time-Dependent Density Functional Theory: Formalism and Applications to Core-Excited States

Abstract

The particle-hole interaction problem is longstanding within time-dependent density functional theory (TDDFT) and leads to extreme errors in the prediction of K-edge X-ray absorption spectra (XAS). We derive a linear-response formalism that uses optimized orbitals of the n-1-electron system as reference, building orbital relaxation and a proper hole into the initial density. Our approach is an exact generalization of the static-exchange approximation that ameliorates particle-hole interaction error associated with the adiabatic approximation and reduces errors in TDDFT XAS by orders of magnitude. With a statistical performance of just 0.5 eV root-mean-square error and the same computational scaling as TDDFT under the core-valence separation approximation, we anticipate that this approach will be of great utility in XAS calculations of large systems.

11 pages (main text), 12 pages (supporting information), 9 figures

References in corpus (11)

• Time-dependent density functional theory: Past, present, and future
• 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
• Charge-Transfer in Time-Dependent Density Functional Theory
• Low-scaling $GW$ with benchmark accuracy and application to phosphorene nanosheets
• Efficient Simulation of Near-Edge X-ray Absorption Fine Structure (NEXAFS) in Density-Functional Theory: Comparison of Core-Level Constraining Approaches
• Relativistic Orbital Optimized Density Functional Theory for Accurate Core-Level Spectroscopy
• Direct observation of charge separation in an organic light harvesting system by femtosecond time-resolved XPS
• Reliable transition properties from excited-state mean-field calculations
• First principles correction scheme for linear-response time-dependent density functional theory calculations of core electronic states
• Computing X-ray absorption spectra from linear-response particles atop optimized holes

Cited by in corpus (3)

• Generalization of one-center non orthogonal configuration interaction singles to open shell singlet reference states: Theory and application to valence-core pump-probe states in acetylacetone
• Measurement of Coherent Vibrational Dynamics with X-ray Transient Absorption Spectroscopy Simultaneously at the Carbon K- and Chlorine L${}_{2,3}$- Edges
• Explicit core-hole single-particle methods for L- and M- edge X-ray absorption and electron energy-loss spectra