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

Autor:	Carter-Fenk, Kevin, Cunha, Leonardo A., Arias-Martinez, Juan E., Head-Gordon, Martin
Rok vydání:	2022
Předmět:	Physics - Chemical Physics Physics - Computational Physics Quantum Physics
Druh dokumentu:	Working Paper
DOI:	10.1021/acs.jpclett.2c02564
Popis:	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. Comment: 11 pages (main text), 12 pages (supporting information), 9 figures
Databáze:	arXiv
Externí odkaz:	http://arxiv.org/abs/2205.08658 Zobrazit plný text záznamu View this record from Arxiv