Quantifying van der Waals Interactions in Layered Transition Metal Dichalcogenides from Pressure-Enhanced Valence Band Splitting

van der Waals (vdW) forces, despite being relatively weak, hold the layers together in transition metal dichalcogenides (TMDs) and play a key role in their band structure evolution, hence profoundly affecting their physical properties. In this work, we experimentally probe the vdW interactions in MoS2 and other TMDs by measuring the valence band maximum (VBM) splitting (Δ) at K point as a function of pressure in a diamond anvil cell. As high pressure increases interlayer wave function coupling, the VBM splitting is enhanced in 2H-stacked MoS2 multilayers but, due to its specific geometry, not in 3R-stacked multilayers, hence allowing the interlayer contribution to be separated out of the total VBM splitting, as well as predicting a negative pressure (2.4 GPa) where the interlayer contribution vanishes. This negative pressure represents the threshold vdW interaction beyond which neighboring layers are electronically decoupled. This approach is compared to first-principles calculations and found to be widely applicable to other group-VI TMDs.