High-harmonic spectroscopy of transient two-center interference calculated with time-dependent density-functional theory.

We demonstrate high-harmonic spectroscopy in many-electron molecules using time-dependent density-functional theory. We show that a weak attosecond-pulse-train ionization seed that is properly synchronized with the strong driving mid-infrared laser field can produce experimentally relevant high-harmonic generation (HHG) signals, from which we extract both the spectral amplitude and the target-specific phase (group delay). We also show that further processing of the HHG signal can be used to achieve molecular-frame resolution, i.e., to resolve the contributions from rescattering on different sides of an oriented molecule. In this framework, we investigate transient two-center interference in CO2 and OCS, and how subcycle polarization effects shape the oriented/aligned angle-resolved spectra.

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

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.