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Theoretical calculations have been carried out to investigate the possible dissociation channels of isoprene. We focus on the major fragment ions of C5H7+, C5H5+, C4H5+, C3H6+, C3H5+, C3H4+, C3H3+ and C2H3+, which were observed experimentally from the isoprene dissociative photoionization. The energy calculations were performed with the CBS-QB3 model. All the geometries and energies of the fragments, intermediates and transition states involved in the dissociations channels were determined. Finally, the mechanisms of the dissociation pathways were discussed on the comparison of theoretical and experimental results.

The gas phase hydration of glyoxal (HCOCHO) in the presence of sulfuric acid (H2SO4) were studied by the high-level quantum chemical calculations with M06-2X and CCSD(T) theoretical methods and the conventional transition state theory (CTST). The mechanism and rate constant of the five different reaction paths are considered corresponding to HCOCHO+H2O, HCOCHO+H2O⋯H2O, HCOCHO⋯H2O+H2O, HCOCHO+H2O⋯H2SO4 and HCOCHO⋯H2O+H2SO4. Results show that H2SO4 has a strong catalytic ability, which can significantly reduce the energy barrier for the hydration reaction of glyoxal. The energy barrier of hydrolysis of glyoxal in gas phase is lowered to 7.08 kcal/mol from 37.15 kcal/mol relative to pre-reactive complexes at the CCSD(T)/6-311++G(3df, 3pd)//M06-2X/6-311++G(3df, 3pd) level of theory. The rate constant of the H2SO4 catalyzed hydrolysis of glyoxal is 1.34×10−11 cm3/(molecule·s), about 1013 higher than that involving catalysis by an equal number of water molecules, and is greater than the reaction rate of glyoxal reaction with OH radicals of 1.10×10−11 cm3/(molecule·s) at the room temperature, indicating that the gas phase hydrolysis of glyoxal of H2SO4 catalyst is feasible and could compete with the reaction glyoxal+OH under certain atmospheric conditions. This study may provide useful information on understanding the mechanistic features of inorganic acid-catalyzed hydration of glyoxal for the formation of oligomer.

Neuromorphic computing has the potential to accelerate high performance parallel and low power in-memory computation, artificial intelligence, and adaptive learning. Despite emulating the basic functions of biological synapses well, the existing artificial electronic synaptic devices have yet to match the softness, robustness, and ultralow power consumption of the brain. Here, we demonstrate an all-inorganic flexible artificial synapse enabled by a ferroelectric field effect transistor based on mica. The device not only exhibits excellent electrical pulse modulated conductance updating for synaptic functions but also shows remarkable mechanical flexibility and high temperature reliability, making robust neuromorphic computation possible under external disturbances such as stress and heating. Based on its linear, repeatable, and stable long-term plasticity, we simulate an artificial neural network for the Modified National Institute of Standards and Technology handwritten digit recognition with an accuracy of 94.4%. This work provides a promising way to enable flexible, low-power, robust, and highly efficient neuromorphic computation that mimics the brain.

Chlorine dioxide (OClO) is an important indicator for Cl‐activation. The monitoring of OClO appears to be crucial for understanding the chemistry of Cl‐initialed oxidation and its impact on air quality in polluted coastal regions and industrialized areas. We report the development of a Xe arc lamp based near‐ultraviolet (335–375 nm) incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) spectrometer for quantitative assessment of OClO in an atmospheric simulation chamber. The important intermediate compound CH2O, and other key atmospheric trace species (NO2) were also simultaneously measured. The instrumental performance shows a strong potential of this kind of IBBCEAS instrument for field and laboratory studies of atmospheric halogen chemistry.

The composition of products formed from photooxidation of the aromatic hydrocarbon toluene was investigated. The OH-initiated photooxidation experiments were conducted by irradiating toluene/CH3ONO/NO/air mixtures in a smog chamber, the gaseous products were detected under the supersonic beam conditions by utilizing vacuum ultraviolet photoionization mass spectrometer using synchrotron radiation in real-time. And an aerosol time-of-flight mass spectrometer was used to provide on-line measurements of the individual secondary organic aerosol particle resulting from irradiating toluene. The experimental results demonstrated that there were some differences between the gaseous products and that of particle-phase, the products of glyoxal, 2-hydroxyl-3-oxo-butanal, nitrotoluene, and methyl-nitrophenol only existed in the particle-phase. However, furane, methylglyoxal, 2-methylfurane, benzaldehyde, cresol, and benzoic acid were the predominant photooxidation products in both the gas phase and particle phase.

The interconversion between the two distinct isomers of methyl vinyl ether (MVE), the formation of the primary ozonides from O3-initated reactions of MVE, the transformation between the primary ozonides, and the subsequent fragmentation were studied using quantum chemical methods at the BHandHLYP/6–311++G(d,p) level of theory for optimized geometries and frequency calculations and at the QCISD/6–31G(d,p) level for the single point energy calculations. The rate coefficients were calculated for the temperature range 280–440 K by using the canonical transition state theory (TST). For ozone addition to MVE, there are two different possibilities discussed on the basis of two different possible orientations for ozone attack. The results of the theoretical study indicate that although the synperiplanar-MVE is 7.11 kJ/mol more stable than the antiperiplanar-MVE, the antiperiplanar-MVE plays a more important role in formation of the primary ozonides because the primary ozonides formed from the ozone addition antiperiplanar-MVE are more stable and the energy barriers corresponding to transition states are lower. The interconversion between the primary ozonides formed from the ozone addition to antiperiplanar-MVE is the most accessible compared with the transformations between other primary ozonides. The cleavage of the primary ozonides mainly leads to the formation of the CH2OO, which is in agreement with the experimental estimates. The calculated overall rate constant for the ozone-initiated reactions is 4.8×10−17cm3/(molecules) at 298.15 K, which agrees with the experimental value for ethyl vinyl ether.

Black phosphorus is a layered material stacked together by weak van der Waals force with a direct bandgap and highly anisotropic electrical characteristics. Most of the previous reports focus on the low-field mobility of transistors based on SiO2 back gate dielectrics. Recently, black phosphorus transistors encapsulated with hexagonal boron nitride have been demonstrated with greatly improved mobility at low temperatures. However, this approach requires multiple dry transfer methods using both black phosphorus and boron nitride flakes, which are only available in small crystal sizes. Here, we demonstrated high performance black phosphorus transistors using atomic layer deposited high-κ HfO2 as a back gate dielectric. The maximum drain current density reaches 480 μA/μm at 300 K and a record high drain current 906 μA/μm at 20 K in a short channel 100 nm device based on HfO2, exhibiting excellent current-carrying capability and high field strength. Moreover, a side-by-side comparison on important figures-of-...