Unraveling the interlayer and intralayer coupling in two-dimensional layered MoS2 by X-ray absorption spectroscopy and ab initio molecular dynamics simulations

Understanding interlayer and intralayer coupling in two-dimensional layered materials (2DLMs) has fundamental and technological importance for their large-scale production, engineering heterostructures, and development of flexible and transparent electronics. At the same time, the quantification of weak interlayer interactions in 2DMLs is a challenging task, especially, from the experimental point of view. Herein, we demonstrate that the use of X-ray absorption spectroscopy in combination with reverse Monte Carlo (RMC) and ab initio molecular dynamics (AIMD) simulations can provide useful information on both interlayer and intralayer coupling in 2DLM 2H_c-MoS₂. The analysis of the low-temperature (10–300 K) Mo K-edge extended X-ray absorption fine structure (EXAFS) using RMC simulations allows for obtaining information on the means-squared relative displacements σ² for nearest and distant Mo–S and Mo–Mo atom pairs. This information allowed us further to determine the strength of the interlayer and intralayer interactions in terms of the characteristic Einstein frequencies ω_E and the effective force constants κ for the nearest ten coordination shells around molybdenum. The studied temperature range was extended up to 1200 K employing AIMD simulations which were validated at 300 K using the EXAFS data. Both RMC and AIMD results provide evidence of the reduction of correlation in thermal motion between distant atoms and suggest strong anisotropy of atom thermal vibrations within the plane of the layers and in the orthogonal direction.