Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core-valence correlation, large basis sets, and extrapolation to the CBS limit to provide benchmark values for Diels-Alder transition states leading to competitive strained pentacyclic adducts. We then used those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are ωB97M-V, M11plus, ωB97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. These findings can guide selection of density functionals for future studies of crowded, strained transition states of large molecules.
The Rayleigh-Taylor Instability (RTI) under multi-mode perturbation in compressible flow is probed via the Discrete Boltzmann Modeling (DBM) with tracers. The distribution of tracers provides clear boundaries between light and heavy fluids in the position space. Besides, the position-velocity phase space offers a new perspective for understanding the flow behavior of RTI with intuitive geometrical correspondence. The effects of viscosity, acceleration, compressibility, and Atwood number on the mixing of material and momentum and the mean non-equilibrium strength at the interfaces are investigated separately based on both the mixedness defined by the tracers and the non-equilibrium strength defined by the DBM. The mixedness increases with viscosity during early stage but decreases with viscosity at the later stage. Acceleration, compressibility, and Atwood number show enhancement effects on mixing based on different mechanisms. After the system relaxes from the initial state, the mean non-equilibrium strength at the interfaces presents an initially increasing and then declining trend, which is jointly determined by the interface length and the macroscopic physical quantity gradient. We conclude that the four factors investigated all significantly affect early evolution behavior of RTI system, such as the competition between interface length and macroscopic physical quantity gradient. The results contribute to the understanding of the multi-mode RTI evolutionary mechanism and the accompanied kinetic effects.
Filter bank multi-carrier (FBMC) can provide higher spectral efficiency and lower out-of-band spectrum leakages than orthogonal frequency division multiplexing (OFDM) or discrete multi-tone (DMT). Due to a crystal or oscillator usually having a frequency tolerance and stability of a few tens of parts per million (ppm), the sampling frequency offset (SFO) between digital-to-analog converter and analog-to-digital converter in the transceiver will seriously degrade the performance of these asynchronous optical multi-carrier communication systems. The SFO-induced impairments and their estimation and compensation methods have been widely studied in optical OFDM/DMT systems. However, the SFO problem is rarely investigated in the optical fiber FBMC system. In this work, the SFO-induced impairments in the asynchronous optical FBMC system are first theoretically analyzed, and then we propose an inter-symbol guard (ISG) and training symbol (TS)-aided SFO estimation method and compare two commonly used SFO compensation methods, i.e., phase compensation (PC) and digital interpolation (DI) regarding estimation accuracy and bit error rate (BER) or error vector magnitude performance by both numerical simulation and offline experiment. The results exhibit that an SFO estimation accuracy of less than ±1 ppm is achieved in the intensity modulation and direct detection FMBC system with a 20-km single-mode fiber link under initial SFOs up to ±200 ppm. Besides, FBMC can afford a similar BER performance with DMT with PC or DI methods in the presence of SFO up to ±100 ppm, and achieve a negligible power penalty at the BER of 3.8e-3, compared to the SFO-free cases. Moreover, FBMC is more robust to SFO estimation errors than DMT.
Computational investigations on the BPE-ligated Cu-catalysed enantioselective addition of enynes to ketones were performed with DFT method. Two BPE-CuMes catalysts, BPE-CuMes and (S,S)-Ph-BPE–CuMes, were employed to probe the reaction mechanism with the emphasis on stereoselectivity. The calculations on the BPE-CuMes system indicate that the actvie metallized enyne intermediate acts as the catalyst for the catalytic cycle. The catalytic cycle involves two steps: 1) the ketone addition to the alkene moiety of the metallized enyne; 2) the metallization of enyne followed by the release of product with the recovery of the active metallized enyne intermediate. The first step accounts for the distribution of the products, and therefore is the stereo-controlling step in chiral systems. In the chiral (S,S)-Ph-BPE–CuMes system, the steric hindrance is vital for the distribution of products and responsible for the stereoselectivity of this reaction. The steric hindrance between the phenyl ring of the two substrates and groups at the chiral centers in the ligand skeleton is identified as the original of the stereoselectivity for the titled reaction.
Methanol-to-olefins (MTO) is a very important industrial catalysis technique for the production of light olefins, which is of great economic value and strategic significance. However, it is a great challenge for the traditional analytical methods to obtain the real-time information of product variation during MTO reaction process, which is vital for the conversion process research and mechanism explanation. In this study, a single photon ionization time-of-flight mass spectrometry (SPI-TOFMS) based on a windowless RF-discharge (WLRF) lamp was developed for real-time measurement of catalytic product during the initial stage of MTO reaction. The vacuum ultraviolet (VUV) photon energy was easily adjusted by changing the discharge gas. Argon (Ar) gas was eventually adopted as the discharge gas, since it produces photons with appropriate energy of 11.6 eV and 11.8 eV for ionization of light olefin molecules. The detection sensitivities of ethylene and propylene were largely improved to a substantially similar level with limits of detection (LODs) down to 16.98 and 9.64 ppbv, respectively. The initial stage of MTO reaction was real-time monitored with a high temporal resolution of 0.5 s, revealing that ethylene was the first olefin product followed by propylene. The successful application of WLRF-SPI-TOFMS in the monitoring of MTO catalytic process indicated broad application prospects of this instrument in the industrial reaction process monitoring.
Computational investigations on the bisphospholanoethane (BPE)-ligated Cu-catalyzed enantioselective addition of enynes to ketones were performed with the density functional theory (DFT) method. Two BPE-mesitylcopper (CuMes) catalysts, BPE-CuMes and (S,S)-Ph-BPE–CuMes, were employed to probe the reaction mechanism with the emphasis on stereoselectivity. The calculations on the BPE-CuMes system indicate that the active metallized enyne intermediate acts as the catalyst for the catalytic cycle. The catalytic cycle involves two steps: (1) ketone addition to the alkene moiety of the metallized enyne; and (2) metallization of the enyne followed by the release of product with the recovery of the active metallized enyne intermediate. The first step accounts for the distribution of the products, and therefore is the stereo-controlling step in chiral systems. In the chiral (S,S)-Ph-BPE–CuMes system, the steric hindrance is vital for the distribution of products and responsible for the stereoselectivity of this reaction. The steric hindrance between the phenyl ring of the two substrates and groups at the chiral centers in the ligand skeleton is identified as the original of the stereoselectivity for the titled reaction.
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