Thermodynamic equilibrium between locally excited and charge-transfer states through thermally activated charge transfer in 1-(pyren-2′-yl)-o-carborane

Reversible conversion between excited-states plays an important role in many photophysical phenomena. Using 1-(pyren-2′-yl)-o-carborane as a model, we studied the photoinduced reversible charge-transfer (CT) process and the thermodynamic equilibrium between the locally-excited (LE) state and CT state, by combining steady state, time-resolved, and temperature-dependent fluorescence spectroscopy, fs- and ns-transient absorption, and DFT and LR-TDDFT calculations. Our results show that the energy gaps and energy barriers between the LE, CT, and a non-emissive ‘mixed’ state of 1-(pyren-2′-yl)-o-carborane are very small, and all three excited states are accessible at room temperature. The internal-conversion and reverse internal-conversion between LE and CT states are significantly faster than the radiative decay, and the two states have the same lifetimes and are in thermodynamic equilibrium.

Reversible conversion between excited-states is key to many photophysical phenomena. We studied the equilibrium between LE and CT states by time-resolved and temperature-dependent fluorescence, fs- and ns-transient absorption, and LR-TDDFT calculations.     

实现冷原子或冷分子囚禁的双层光阱列阵

提出了一种新颖的实现冷原子或冷分子囚禁的双层光阱方案,它由二元π相位板列阵和会聚透镜列阵所组成,用平面光波通过此光学系统时将在透镜焦平面两侧形成双层光阱.介绍了产生双层光阱的基本原理,分析了光阱光强分布、强度梯度等与光学系统参数间的关系,研究了双层光阱囚禁原子(或分子)的光学偶极势和自发散射速率(包括瑞利散射和拉曼散射)等.该方案不仅可用于多样品原子(或分子)的光学囚禁及全光型玻色一爱因斯坦凝聚(BEC),而且可用于制备新颖的双层2D光学晶格.     

空间太阳电池槽式聚光热电联供系统特性分析

建立了空间太阳电池的热电联供系统在槽式聚光条件下的热电性能模型, 并与实验进行了对比.理论计算与实验结果吻合较好, 最大误差在5.1%以内, 证明了该数学模型的正确性.通过此数学模型, 从聚光镜面的光学效率与焦线宽度、导热胶的导热系数、金属平板光照面的吸收率等内部特性参数及风速、太阳直辐射等外部特性参数出发, 对所设计制造的空间太阳电池槽式聚光热电联供系统进行分析.较为全面而系统地分析了这些参数的改变对其系统的热电效率、总效率及火用效率等性能指标的影响, 其中聚光镜面的光学效率影响最大, 光学效率从0.5增加至0.95, 系统的总效率和火用效率分别增加0.9倍和0.5倍, 其余参数对性能也有较强影响.研究结果为新一轮系统装置的制作提供了优化设计基础.     

求解中国农业困局：国际视野中的农业规模经营与农业竞争力

近年来中国粮食生产出现的“高产量、高库存、高进口”现象,是由于农均耕地面积过小引起的规模经营不足。这背后,是户籍制度造成的城市化滞后以及针对外来人口的公共服务不平等。同时,政府大力补贴农业和农村,提高了农民向城市转移的机会成本,导致土地流转率不足,进一步阻碍规模经营。通过国际比较,我们认为规模化农场有利于提高农业竞争力,而小农经济现代化的成本较高。研究还发现,在世界范围内,农业劳动力转移适应农业产出比重下降的国家拥有更大的农均在（可）耕地,它对农均粮食净出口存在显著正效应。反事实分析说明,若中国2011年的农业就业比重能和产出比重相适应（即消除城乡间劳动力流动障碍）,则下一年粮食净输入将下降约89%。     

创新导向减税与就业结构升级—基于研发费用加计扣除的检验

创新在中国经济社会发展中的作用愈发突出,如何促进高技能劳动力向创新主体部门集聚,值得深入探索。基于2018年企业所得税研发费用加计扣除比例提升冲击,利用A股上市公司2016−2019年数据,本文研究了创新导向减税对就业结构的影响。研究发现,加计扣除比例提升显著提高了企业雇佣劳动力中研究生所占比例,促进了企业创新人力资本积累。异质性分析显示,政策在非公有制企业、主板上市企业中效果更明显。对企业各层次雇佣规模的评估表明,雇佣总量及研究生、本科生雇佣数均有所提高,同时本科以下学历人员并未明显减少,这意味着政策未产生明显的挤出效应,高技能劳动力雇佣的增加并不以低技能劳动力的减少为代价。综合来看,政策不但能促进企业加大研发投入,还有助于提高全要素生产率和盈利水平。本文结论为通过实施结构性减税,推动创新驱动发展提供了经验支撑。     

Enzymatic Synthesis of a Diastereomer of Neoabyssomicin Derivative Using the Diels-Alderase AbyU

Main observation and conclusion The enzyme AbyU catalyses a Diels-Alder (DA) reaction during abyssomicin C biosynthesis.In this study,AbyU is shown to convert t...     

Enantioselective Organocatalytic Aza-Michael Additions of Phthalimide Derivatives to α,β-Unsaturated Aldehydes

Phthalimide derivatives as nitrogen nucleophiles with α,β‐unsaturated aldehydes for asymmetric aza‐Michael additions have been reported. The reactions proceed smoothly to afford corresponding Michael adducts in good yields (up to 98%) and enantioselectivities (up to 95% ee).     

Computational studies on 3,5,7,10,12,14,15,16-octanitro-3,5,7,10,12,14,15,16-octaaza-pentacyclo[7.5.1.12,8.04,13.06,11]hexadecane as potential high-energy-density compound

The B3LYP/6-31G(d) method of density functional theory was used to study molecular geometry, electronic structure, infrared spectrum, and thermodynamic properties. Detonation properties were evaluated using Kamlet–Jacobs equations based on the calculated density and heat of formation. Thermal stability of 3,5,7,10,12,14,15,16-octanitro-3,5,7,10,12,14,15,16-octaaza-pentacyclo[7.5.1.1^2,8.0^4,13.0^6,11]hexadecane (cage-HMX) was investigated by calculating the bond dissociation energy at unrestricted B3LYP/6-31G(d) level. The calculated results show that the first step of pyrolysis is the rupture of the N–NO₂ bond. The crystal structure obtained by molecular mechanics belongs to P2₁ space group, with lattice parameters a = 8.866 Å, b = 11.527 Å, c = 13.011 Å, Z = 4, and ρ = 2.219 g cm^?3. Both the detonation velocity of 9.79 km s^?1 and the detonation pressure of 45.45 GPa are better than those of CL-20. According to the quantitative standard of energetics and stability as a high-energy-density compound, cage-HMX essentially satisfies this requirement. These results provide basic information for molecular design of novel HEDCs.