Directional charge delocalization dynamics in semiconducting 2H-MoS[Formula: see text] and metallic 1T-Li[Formula: see text]MoS[Formula: see text].

The layered dichalcogenide MoS[Formula: see text] is relevant for electrochemical Li adsorption/intercalation, in the course of which the material undergoes a concomitant structural phase transition from semiconducting 2H-MoS[Formula: see text] to metallic 1T-Li[Formula: see text]MoS[Formula: see text]. With the core hole clock approach at the S L[Formula: see text] X-ray absorption edge we quantify the ultrafast directional charge transfer of excited S3p electrons in-plane ([Formula: see text]) and out-of-plane ([Formula: see text]) for 2H-MoS[Formula: see text] as [Formula: see text] fs and [Formula: see text] fs and for 1T-Li[Formula: see text]MoS[Formula: see text] as [Formula: see text] fs and [Formula: see text] fs. The isotropic charge delocalization of S3p electrons in the semiconducting 2H phase within the S-Mo-S sheets is assigned to the specific symmetry of the Mo-S bonding arrangement. Formation of 1T-Li[Formula: see text]MoS[Formula: see text] by lithiation accelerates the in-plane charge transfer by a factor of [Formula: see text] due to electron injection to the Mo-S covalent bonds and concomitant structural repositioning of S atoms within the S-Mo-S sheets. For excitation into out-of-plane orbitals, an accelerated charge transfer by a factor of [Formula: see text] upon lithiation occurs due to S-Li coupling.