Long range piezoelectricity effects in van der Waals heterobilayer systems beyond 1000 atoms.

Twist angle is a relevant design and control component for the piezoelectric coefficients of van der Waals (vdW) heterostructures. This theoretical work assesses in high detail the impact of the twist angle on the piezoelectricity of two-dimensional (2D) heterobilayer systems. We expand the density-functional based tight-binding method to predict the piezoelectric coefficients of twisted and corrugated 2D heterobilayer structures with more than 1000 atoms. We showcase the method on hexagonal III-V/transition metal dichalcogenide vdW heterosystems. Our calculations yield a periodic relationship between the in-plane piezoelectric coefficients and the corresponding twist angles, indicating the tunability of the in-plane piezoelectricity. In contrast, the out-of-plane piezoelectricity is not twist angle dependent, but nonlinearly changes with the average interlayer distance.

Quantum Mechanical Modeling of Reaction Rate Acceleration in Microdroplets.

Organic reactions in microdroplets can be orders of magnitude faster than their bulk counterparts. We hypothesize that solvation energy differences between bulk and interface play a key role in the intrinsic rate constant increase and test the hypothesis with explicit solvent calculations. We demonstrate for both the protonated phenylhydrazine reagent and the hydrazone transition state (TSB) that molecular orientations which place the charge sites at the surface confer high energy. A pathway in which this high-energy form transforms into a fully solvated TSB has a lower activation energy than bulk by some 59 kJ/mol, a result that is consistent with experimental rate acceleration studies.