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Ionic reactions are the most common reactions used in chemical synthesis. In relatively low dielectric constant solvents (e.g., dichloromethane, toluene), ions usually exist as ion pairs. Despite the importance of counterions, a quantitative description of how the paired ’counterion’ affects the reaction kinetic is still elusive. We introduce a general and quantitative model, namely transition-state expansion (TSE), that describes how the size of a counterion affects the transition- state structure and the kinetics of an ionic reaction. This model could rationalize the counterion effects in nucleophilic substitutions and gold-catalyzed enyne cycloisomerizations. 

Antiferromagnets are interesting materials for spintronics because of their faster dynamics and robustness against perturbations from magnetic fields. Control of the antiferromagnetic order constitutes an important step towards applications, but has been limited to bulk materials so far. Here, using spatially resolved second-harmonic generation, we show direct evidence of long-range antiferromagnetic order and Ising-type Néel vector switching in monolayer MnPSe3 with large XY anisotropy. In additional to thermally induced switching, uniaxial strain can rotate the Néel vector, aligning it to a general in-plane direction irrespective of the crystal axes. A change of the universality class of the phase transition in the XY model under uniaxial strain causes this emergence of strain-controlled Ising order in the XY magnet MnPSe3. Our discovery is a further ingredient for compact antiferromagnetic spintronic devices in the two-dimensional limit. 

Amorphous solids lack long-range order. Therefore identifying structural defects—akin to dislocations in crystalline solids—that carry plastic flow in these systems remains a daunting challenge. By comparing many different structural indicators in computational models of glasses, under a variety of conditions we carefully assess which of these indicators are able to robustly identify the structural defects responsible for plastic flow in amorphous solids. We further demonstrate that the density of defects changes as a function of material preparation and strain in a manner that is highly correlated with the macroscopic material response. Our work represents an important step towards predicting how and when an amorphous solid will fail from its microscopic structure. 

Stratified random sampling (SRS) is a widely used sampling technique for approximate query processing. We consider SRS on continuously arriving data streams, and make the following contributions. We present a lower bound that shows that any streaming algorithm for SRS must have (in the worst case) a variance that is Ω(r) factor away from the optimal, where r is the number of strata. We present S-VOILA, a streaming algorithm for SRS that is locally variance-optimal. Results from experiments on real and synthetic data show that S-VOILA results in a variance that is typically close to an optimal offline algorithm, which was given the entire input beforehand. We also present a variance-optimal offline algorithm VOILA for stratified random sampling. VOILA is a strict generalization of the well-known Neyman allocation, which is optimal only under the assumption that each stratum is abundant, i.e. has a large number of data points to choose from. Experiments show that VOILA can have significantly smaller variance (1.4x to 50x) than Neyman allocation on real-world data.