Directional sub-femtosecond charge transfer dynamics and the dimensionality of 1T-TaS₂

For the layered transition metal dichalcogenide 1T-TaS₂, we establish through a unique experimental approach and density functional theory, how ultrafast charge transfer in 1T-TaS₂ takes on isotropic three-dimensional character or anisotropic two-dimensional character, depending on the commensurability of the charge density wave phases of 1T-TaS₂. The X-ray spectroscopic core-hole-clock method prepares selectively in- and out-of-plane polarized sulfur 3p orbital occupation with respect to the 1T-TaS₂ planes and monitors sub-femtosecond wave packet delocalization. Despite being a prototypical two-dimensional material, isotropic three-dimensional charge transfer is found in the commensurate charge density wave phase (CCDW), indicating strong coupling between layers. In contrast, anisotropic two-dimensional charge transfer occurs for the nearly commensurate phase (NCDW). In direct comparison, theory shows that interlayer interaction in the CCDW phase - not layer stacking variations - causes isotropic three-dimensional charge transfer. This is presumably a general mechanism for phase transitions and tailored properties of dichalcogenides with charge density waves.