Polarization-Resolved Core Exciton Dynamics in LiF Using Attosecond Transient Absorption Spectroscopy

The ability to control absorption by modifying the polarization of light presents an exciting opportunity to experimentally determine the orbital alignment of absorption features. Here, attosecond extreme ultraviolet (XUV) transient absorption spectroscopy is used to investigate the polarization dependence of core exciton dynamics in LiF thin films at the Li+ K edge. XUV pulses excite electrons from the Li 1s core level into the conduction band, allowing for the formation of a p-orbital-like core exciton, aligned along the XUV light polarization axis. A sub-5 fs near-infrared (NIR) probe pulse then arrives at variable time delays, perturbing the XUV-excited states and allowing the coherence decay of the core exciton to be mapped. The coherence lifetimes are found to be ~2.4 +- 0.4 fs, which is attributed to a phonon-mediated dephasing mechanism as in previous core exciton studies. The differential absorption features are also shown to be sensitive to the relative polarization of the XUV and NIR fields. The parallel NIR probe induces couplings between the initial XUV-excited p-like bright exciton and s-like dark excitons. When crossed pump and probe polarizations are used, the coupling between the bright and dark states is no longer dipole-allowed, and the transient absorption signal associated with the coupling is suppressed by approximately 90%. This interpretation is supported by simulations of a few-level model system, as well as analysis of the calculated band structure. The results indicate that laser polarization can serve as a powerful experimental tool for exploring the orbital alignment of core excitonic states in solid-state materials.
Comment: 18 pages, 14 figures