At present, the reactivity of cyclic alkanes is estimated by comparison with acyclic hydrocarbons. Due to the difference in the structure of cycloalkanes and acycloalkanes, the thermodynamic data obtained by analogy are not applicable. In this study, a molecular beam sampling vacuum ultraviolet photoionization time-of-flight mass spectrometer (MB-VUV-PI-TOFMS) was applied to study the low-temperature oxidation of cyclopentane (CPT) at a total pressure range from 1–3 atm and low-temperature range between 500 and 800 K. Low-temperature reaction products including cyclic olefins, cyclic ethers, and highly oxygenated intermediates (e. g., ketohydroperoxide KHP, keto-dihydroperoxide KDHP, olefinic hydroperoxides OHP and ketone structure products) were observed. Further investigation of the oxidation of CPT – electronic structure calculations – were carried out at the UCCSD(T)-F12a/aug-cc-pVDZ//B3LYP/6-31+ G(d,p) level to explore the reactivity of O2 molecules adding sequentially to cyclopentyl radicals. Experimental and theoretical observations showed that the dominant product channel in the reaction of CPT radicals with O2 is HO2 elimination yielding cyclopentene. The pathways of second and third O2 addition – the dissociation of hydroperoxide – were further confirmed. The results of this study will develop the low-temperature oxidation mechanism of CPT, which can be used for future research on accurately simulating the combustion process of CPT. 相似文献
Laser cooling of a molecule with heavy nuclei is often complicated because of the density distribution of the electronic states. Here, we evaluate the feasibility of the laser cooling of the SrI molecule by calculating the potential energy curves and transition dipole moments of the ground and low-lying excited states using the multi-reference configuration interaction plus Davidson corrections (MRCI + Q) and the all-electron basis sets of ANO-RCC. The relativistic effect and the spin-orbit coupling splits are included, because both Sr and I are heavy atoms. Based on the obtained potential energy curves, we solve the Schrödinger equation of nuclear motion to determine the rovibrational energy levels and the Franck-Condon factors. The spectroscopic parameters are obtained by fitting the rovibrational energy levels with the Dunham expression. The radiation lifetimes, the Doppler and recoil temperatures between the X2Σ+ and the 2Π1/2/2Π3/2/B2Σ+ states are calculated. 5-color laser cooling schemes for the molecule are proposed, which can lead to the total effective Franck-Condon factors being 0.99983, 0.99979, and 0.99941 for the three transitions, respectively. All the obtained results suggest that the SrI molecule is a feasible candidate for laser cooling. 相似文献
A solution to the problem of Gaussian beam scattering by an anisotropically coated circular cylinder is presented. The incident Gaussian beam source is expanded as an approximate expression in the simple form with a Tayor’s series. The transmitted field in the anisotropically coated region is expressed as a infinite summation of eigen plane waves with different polar angles. The unknown coefficients of the scattered fields are obtained with the aid of the boundary conditions. The infinite series can be truncated under the prerequisite of achieving the solution convergence. Only the case of transverse-electric polarization is discussed. The similar formulation of transverse-magnetic polarization can be obtained by adopting the similar method. Some numerical results are presented and discussed. The result is in agreement with that available as expected when the Gaussian beam degenerates to a plane wave incidence case. 相似文献
The high-pressure structures and properties of MH2 (M = Nb, Ta) are explored through an ab initio evolutionary algorithm for crystal structure prediction and first-principles calculations. It is found that NbH2 undergoes a phase transition from a cubic Fmm structure with regular NbH8 cubes to an orthorhombic Pnma structure with fascinating distorted NbH9 tetrakaidecahedrons at 48.8 GPa, while the phase transition pressure of TaH2 from a hexagonal P63mc phase with slightly distorted TaH7 decahedron to an orthorhombic Pnma phase with attractive distorted TaH9 tetrakaidecahedrons is about 90.0 GPa. Besides, the calculated electronic band structure and density of states demonstrate that all of these structures are metallic. The Poisson’s ratio, electron localization function, and Bader charge analysis suggest that these phases possess dominant ionic bonding character with the effective charges transferring from the metal atom to H. From our electron–phonon calculations, the calculated superconducting critical temperature Tc of the Pnma-NbH2 is 6.903 K at 50 GPa. Finally, via the quasi-harmonic approximation method, the phase diagrams at pressure up to 300 GPa and temperature up to 1000 K of MH2 (M = Nb, Ta) are established, where the transition pressure of Fmm-NbH2 → Pnma-NbH2 and P63mc-TaH2 → Pnma-TaH2 were found to decrease with increasing temperature. 相似文献
Side-chain engineering has been demonstrated as an effective method for fine-tuning the optical, electrical, and morphological properties of organic semiconductors toward efficient organic solar cells (OSCs). In this work, three isomeric non-fullerene small molecule acceptors (SMAs), named BTP-4F-T2C8, BTP-4F-T2EH and BTP-4F-T3EH, with linear and branched alkyl chains substituted on the α or β positions of thiophene as the side chains, were synthesized and systematically investigated. The results demonstrate that the size and substitution position of alkyl side chains can greatly affect the electronic properties, molecular packing as well as crystallinity of the SMAs. After blending with donor polymer D18-Cl, the prominent device performance of 18.25% was achieved by the BTP-4F-T3EH-based solar cells, which is higher than those of the BTP-4F-T2EH-based (17.41%) and BTP-4F-T2C8-based (15.92%) ones. The enhanced performance of the BTP-4F-T3EH-based devices is attributed to its stronger crystallinity, higher electron mobility, suppressed biomolecular recombination, and the appropriate intermolecular interaction with the donor polymer. This work reveals that the side chain isomerization strategy can be a practical way in tuning the molecular packing and blend morphology for improving the performance of organic solar cells.
In this work, a self-heating type optical fiber flowmeter with high sensitivity was proposed. The core-offset fiber structures were employed to couple a part of signal light into the fiber cladding layer, and the other part of light still propagated in the core layer. The intermodal interference between the two parts of light happened when the cladding modes were coupled back into core layer. Meanwhile, the high power laser was also introduced into fiber to heat the silver film coated on the surface of the cladding layer. When the cool gas flow passed, the temperature of the sensor probe decreased due to the heat transfer process. Because of the thermo-optic effect in the fiber, interference spectrum could be shifted when the temperature was changed. The experimental results showed the resolution of the proposed sensor was 2×10−2 m/s in the region of 0–8 m/s. The highest sensitivity could achieve 1537 pm/(m/s). 相似文献
A cobalt-poor or iron rich bicomponent mixture of Co0.9Fe2.1O4/Fe2O3 and Co0.8Fe2.2O4/Fe2O3 anode materials have been successfully prepared using simple, cost-effective, and scalable urea-assisted auto-combustion synthesis. The threshold limit of lower cobalt stoichiometry in CoFe2O4 that leads to impressive electrochemical performance was identified. The electrochemical performance shows that the Co0.9Fe2.1O4/Fe2O3 electrode exhibits high capacity and rate capability in comparison to a Co0.8Fe2.2O4/Fe2O3 electrode, and the obtained data is comparable with that reported for cobalt-rich CoFe2O4. The better rate performance of the Co0.9Fe2.1O4/Fe2O3 electrode is ascribed to its unique stoichiometry, which intimately prefers the combination of Fe2O3 with Co1−xFe2+xO4 and the high electrical conductivity. Further, the high reversible capacity in Co0.9Fe2.1O4/Fe2O3 and Co0.8Fe2.2O4/Fe2O3 electrodes is most likely attributed to the synergistic electrochemical activity of both the nanostructured materials (Co1−xFe2+xO4 and Fe2O3), reaching beyond the well-established mechanisms of charge storage in these two phases. 相似文献
Introducing voids into AlN layer at a certain height using a simple method is meaningful but challenging. In this work, the AlN/sapphire template with AlN interlayer structure was designed and grown by metal-organic chemical vapor deposition. Then, the AlN template was annealed at 1700 ℃ for an hour to introduce the voids. It was found that voids were formed in the AlN layer after high-temperature annealing and they were mainly distributed around the AlN interlayer. Meanwhile, the dislocation density of the AlN template decreased from 5.26×109 cm-2 to 5.10×108 cm-2. This work provides a possible method to introduce voids into AlN layer at a designated height, which will benefit the design of AlN-based devices. 相似文献