The solvent effects for a Claisen rearrangement and a Diels-Alder reaction are investigated. Electronic structure methods are used to generate the frequencies, couplings, and curvatures along the minimum energy paths for these reactions in the gas phase and in the presence of two water molecules. The geometries and charge distributions along the minimum energy paths are analyzed to determine the structural and electrostatic roles of the water molecules. Reactive flux molecular dynamics methods based on a reaction path Hamiltonian are used to calculate the dynamical transmission coefficients, which account for recrossings of the transition state. The transmission coefficients for the Claisen rearrangement are nearly unity both in the gas phase and in the presence of two water molecules. The transmission coefficients for the Diels-Alder reaction are 0.95 and 0.89 in the gas phase and in the presence of two water molecules, respectively. These differences in the transmission coefficients are explained in terms of the locations and magnitudes of the curvature peaks along the reaction path, as well as the shape of the potential energy along the reaction coordinate near the transition state. Analysis of the dynamical trajectories provides insight into the dynamical role of the water molecules and elucidates possible reaction mechanisms.

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Actual origin and precise control of asymmetrical hysteresis in an individual CH3NH3PbI3 micro/nanowire for optical memory and logic operation Runna Gou,a Zhiyong Ouyang,b Changsen Xu,b Song He,a Wei Zeng,a Shouduan...

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Here, CdS@C nanohybrid composites, where CdS quantum dots (QDs) are uniformly embedded in carbon micro-/nanobelt matrixes, are synthesized via a combustion synthesis followed by a postvulcanization. In the nanohybrids, trap centers are effectively created by the introduction of QDs and moreover their barrier height and filling level can be effectively modulated through a coupling of externally loaded strain and bias. Thus, a single CdS@C micro-/nanobelt-based two-terminal device can exhibit an ultrahigh real-time response to compressive and tensile strains with a tremendous gauge factor of above 104, high sensitivity, and fast response and recovery. More importantly, the trapped charges can be mechanically excited by stress, and furthermore, the stress-triggered high-resistance state can be well-maintained at room temperature and a relatively low operation bias. However, it can be back to its initial low resistance state by loading a relatively large bias, showing a superior erasable stress memory function with a window of about 103. By an effective construction of trap centers in hybrid composites, not only can an ultrahigh performance of volatile real-time stress sensor be obtained under the synergism of external stress and electric field but also can an outstanding erasable nonvolatile stress memory be successfully realized.