Pure MgO, ZrO2 and mixture MgO/ZrO2 nanocrystals were annealed in air from 100 to 1200°C. Variation of the microstructure and defects was investigated by positron lifetime spectroscopy and X-ray diffraction. The experiment results showed that the average positron lifetime of mixture MgO/ZrO2 was more larger than that of single phase MgO and ZrO2, and decreased with the increasing annealing temperature. Thermal annealing below 600°C, the movement of grain boundaries mainly led a reduce of the number of microvoids, and vacancy defects began to recover due to the growth of MgO nanoparticles after annealing between 600 to 900°C. Furthermore, ZrO2 nanoparticles began to grow above 900°C, meanwhile the recovery of vacancy and vacancy clusters in MgO/ZrO2 nanoparticles are restrained because of synergic effect between MgO and ZrO2 nanoparticles.
The oxidized Mo-50Re alloys in air at 573 K and 873 K for various times were investigated by X-Ray diffraction and positron annihilation lifetime spectroscopy. The results indicated that main orthogonal phase MoO3 together with small amount of monoclinic phase Mo8O23 were formed on on the surface of the specimens, and the oxide film of specimens oxidized at 873 K were much thicker than that of specimens oxidized at 573 K. Meanwhile, when Mo-50Re specimens oxidized in air at 873K, the defect’s size within interface layer of the specimens was larger, and the oxide film on the surface of the specimens contained much more defects. Faster oxidation process were observed occured at 873K, which was likely due to the formation of larger-size interfacial defects.
The ground state and excited state electronic properties of chlorophyll (Chl) a and Chl b in diethyl ether, acetone, and ethanol solutions are investigated using quantum mechanical and molecular mechanical calculations with density functional theory (DFT) and time-dependent DFT (TDDFT). Although the DFT/TDDFT methods are widely used, the electronic structures of molecules, especially large molecules, calculated with these methods are known to be strongly dependent on the functionals and the parameters used in functionals. Here, we optimize the range-separated parameter, µ, of the CAM-B3LYP functional of Chl a and Chl b to reproduce the experimental excitation energy differences of these Chl molecules in solution. The optimal values of µ for Chl a and Chl b are smaller than the default value of µ and that for bacteriochlorophyll a, indicating the change in electronic distribution, i.e., an increase in electron delocalization, within the molecule. We find that the electronic distribution of Chl b with an extra formyl group is different from that of Chl a. We also find that the polarity of solution and hydrogen bond cause the decrease in the excitation energies and the increase in the widths of excitation energy distributions of Chl a and Chl b. The present results are expected to be useful for understanding the electronic properties of each pigment molecule in a local heterogeneous environment, which will play an important role in the excitation energy transfer in light-harvesting complex II.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.