Attosecond Charge Migration with TDDFT: Accurate Dynamics from a Well-Defined Initial State

• Published in: The journal of physical chemistry letters Vol. 8; no. 17; pp. 3991 - 3996
• Main Authors: Bruner, Adam, Hernandez, Samuel, Mauger, François, Abanador, Paul M, LaMaster, Daniel J, Gaarde, Mette B, Schafer, Kenneth J, Lopata, Kenneth
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07-09-2017
• Subjects: Chemistry; Materials Science; Physics; Science & Technology - Other Topics
• ISSN: 1948-7185; 1948-7185
• DOI: 10.1021/acs.jpclett.7b01652

We investigate the ability of time-dependent density functional theory (TDDFT) to capture attosecond valence electron dynamics resulting from sudden X-ray ionization of a core electron. In this special case the initial state can be constructed unambiguously, allowing for a simple test of the accuracy of the dynamics. The response following nitrogen K-edge ionization in nitrosobenzene shows excellent agreement with fourth-order algebraic diagrammatic construction (ADC(4)) results, suggesting that a properly chosen initial state allows TDDFT to adequately capture attosecond charge migration. Visualizing hole motion using an electron localization picture (ELF), we provide an intuitive chemical interpretation of the charge migration as a superposition of Lewis dot resonance structures.