Tuning the energy level and photophysical and electroluminescent properties of heavy metal complexes by controlling the ligation of the metal with the carbon of the carbazole unit

Four novel Ir-III and Pt-II complexes with cyclometalated ligands bearing a carbazole framework are prepared and characterized by elemental analysis, NMR spectroscopy, and mass spectrometry. Single-crystal X-ray diffraction studies of complexes 1, 3, and 4 reveal that the 3- or 2-position C atom of the carbazole unit coordinates to the metal center. The difference in the ligation position results in significant shifts in the emission spectra with the changes in wavelength being 84 nm for the Ir complexes and 63 nm for the Pt complexes. The electrochemical behavior and photophysical properties of the complexes are investigated, and correlate well with the results of density functional theory (DFT) calculations. Electroluminescent devices with a configuration of ITO/NPB/CBP:dopant/BCP/AlQ(3)/LiF/Al can attain very high efficiencies.

Electronic structures of Al2W, AlW2 clusters and their anions

Possible structures for Al2W and AlW2 clusters and their anions were presented and studied by use of density functional theory B3LYP at various spin multiplicities. The proposed three structures are triangular form with C-2v symmetry; linear structure with D (infinity h) symmetry; and linear structure with C (infinity v) symmetry. The calculated results indicate that structures with C-2v symmetry are the most stable for both neutral clusters and their anions. For Al2W, C-2v Symmetry at spin multiplicity 5 is the ground state, while for its anion, doublet is the lowest. For AlW2 and its anion, doublet and triplet are the ground states, respectively.

Electronic structures of 3d-metal mononitrides

Bond distances, vibrational frequencies, electron affinities, ionization potentials, and dissociation energies of the title molecules in neutral, positively, and negatively charged ions were studied by use of density functional methods B3LYP, BLYP, BHLYP, BPW91, and B3PW91. The calculated results are compared with experiments and previous theoretical studies. It was found that the calculated properties are highly dependent on the functionals employed, in particular for the dissociation energy and vibrational frequency. For neutral species, pure density functional methods BLYP and BPW91 have relatively good performance in reproducing the experimental bond distance and vibrational frequency. For cations, hybrid exchange functional methods B3LYP and B3PW91 are good in predicting the dissociation energy. For both neutral and charged species, BHLYP tends to give smaller dissociation energy.

Chemical bonding and electronic structure of 4d-metal monocarbides

Bond distances, vibrational frequencies, dissociation energies, electron affinities, ionization potentials and dipole moments of the title molecules in neutral and charged ions were studied by use of density functional method. Ground states for each molecule were assigned. For neutral and cationic molecules, the bond distance decreases from YC (YC+) to RhC (RhC+), then increases, while for anionic molecules, the bond distance decreases from YC- to RuC-, then increases. Opposite trend was observed for vibrational frequency. The bond ionic character decreases from ZrC to PdC for neutral molecules. The bonding patterns are discussed and compared with the available studies.

Geometries and electronic properties of Ta-n, TanO and TaOn (n=1-3) clusters

Geometries, vibrational frequencies, electron affinities, ionization potentials and dissociation energies of the title clusters in both neutral and positively and negatively charged states were studied by use of density functional theory. For both neutral and charged species, different initial isomers were studied in order to determine the structure with the lowest energy. Vibrational analysis was also performed in order to characterize these isomers. For Ta-2, Ta-Ta metallic bond is strengthened by adding or removing an electron, i.e. the charged species are much more stable than the neutral counterpart. For Ta-3, equilateral triangle with D-3h symmetry has the lowest energy for both neutral and charged species (near equilateral triangle for cation). TaO and its charged species have much larger dissociation energy compared with other tantalum oxides. For Ta2O and TaO2. structure with C-2v symmetry is much more stable than linear chains. For Ta3O, planar structure with doubly bridging oxygen atoms of C-2v, symmetry is the global minimum for both neutral and charged species. While for TaO3, three-dimensional structures are favored for both neutral (C-1 symmetry) and charged species (C-3v symmetry).

Geometries and electronic properties of AunPdm (n=1-4, m =-1, 0, 1) clusters

Possible conformers for AunPdm (n = 1-4, m = -1, 0, 1) clusters have been presented and studied by use of density functional theory. The results indicate that for n = 2, linear conformer with C-infinityv symmetry is the most stable for anion species, while for cation and neutral species, conformer with C-2v symmetry is the most stable. For n = 3, 4, conformers with C-2v symmetry (kite-shape) are energetically favored. The calculated electron affinities (EAs) and vertical detachment energies (VDEs) are in good agreement with experiments for n = 1-4. It is also interesting to note that for even n (n = 2, 4), the most stable conformers do not give the best agreement between calculated and experimental EA and VDE values, while for odd n (n = 3), the lowest energy conformer also gives the best agreement. The ionization potentials (IPs) of AunPd clusters are calculated as well.

Theoretical investigations of La2C2 cluster

Possible structures of La2C2 were studied and proposed by use of density functional theory. All proposed isomers are planar. The results indicate that the structure with the lowest symmetry (C-1) is the most stable. Linear isomers are not favored.

Thermal stress-induced birefringence in borate glass irradiated by femtosecond laser pulses

Thermal stress-induced birefringence in borate glass which has been irradiated by 800-nm femtosecond laser pulses is observed under cross-polarized light. Due to the high temperature and pressure formed in the focal volume, the material at the edge of the micro-modified region is compressed between the expanding region and the unheated one, then stress emerges. Raman spectroscopy is used to investigate the stress distribution in the micro-modified region and indicates the redistributions of density and refractive index by Raman peak shift. We suggest that this technique can develop waveguide polarizers and Fresnel zone plates in integrated optics.

古田山亚热带常绿阔叶林密度制约普遍性研究

密度制约是否为自然森林维持物种共存的普遍性机制，生态学家对此一直就有争议。目前密度制约的普遍性研究主要集中于热带森林，而针对亚热带森林的研究还比较少见。本文以浙江古田山24 公顷亚热带常绿阔叶林固定监测样地第一次调查数据为基础，主要采用点格局分析的双变量函数g(r)，研究了密度制约是否作用于样地内大部分木本植物，目的在于探讨密度制约在亚热带常绿阔叶林内物种多样性维持中的作用。 检验密度制约效应的常用方法是: 假定在种内竞争、种内个体之间的病虫害传播等条件下，种群的聚集程度是否随年龄的增加而下降。但是生境的异质性也可能导致种群聚集程度的下降。所以在密度制约的普遍性检验之前，首先分析了生境异质性是否影响树木的分布，然后分析种群分布格局，探讨除了生境异质性以外其它影响种群分布的驱动因子，同时为分析密度制约的发生做解释。结果发现生境异质性影响古田山树木的分布。用完全随机零模型不排除异质性，被检验的64个物种几乎在0-30m所有的尺度上都表现聚集。用异质性泊松分布零模型排除异质性，59个被检验物种中58个表现聚集。排不排除异质性，同种聚集都在整个样地中占主要地位，而且随着远离目标个体同种个体的密度逐渐下降，植株主要聚集在同种邻体的周围。结合下面的关联性分析，更新植株主要集中在成年个体周围，说明除了生境异质性效应促进树木聚集分布以外，以繁殖体为中心的局部扩散是大部分物种同种聚集的主要原因。 环境异质性影响树木分布，干扰密度制约的检验。然而，排除生境异质性的影响，也不能肯定密度制约是否是群落物种多样性普遍性的维持机制。用随机标签零模型案例-对照设计，小径级生长阶段的树木格局作为案例，成年树作为对照代表生境异质性的作用，通过小径级树木格局与成年树格局相比，排除生境异质性的干扰，64个被检验物种中50种(78.1%)表现了密度制约稀疏效应。结果表明密度制约稀疏机制调节了样地大部分物种，是古田山亚热带森林群落物种多样性维持的重要机制。同时，密度制约稀疏效应主要发生在局部尺度上，与同种短距离聚集结果一致。另外，密度制约稀疏效应更易于影响丰富种(24公顷样地内个体数>1000)的种群结构。 Janzen-Connell假说的距离制约模型认为繁殖体制约后代更新成功，导致成年树个体间距增大，并得到众多的野外观察证明。然而，在大尺度的森林样地研究中，没有发现这个效应广泛存在。本研究采用独立性零模型分析了不同生活史阶段在空间上的关联性，特别是成年树和幼树、小树的关联性，反过来推演是否成年树对后代的距离制约驱动了种群分布的空间动态。综合分析古田山64个物种的不同径级阶段的空间关联性，同时参照Condit 等(1992，1994)的研究结果：成年树对后代的距离制约效应在小于5m的尺度上发生强烈。有20个物种（31.3%）的更新体聚集密度最高点在离成年树≥5m的距离上，加上21个物种的更新体与成年树的关联性成相互排斥和随机分布，64个被检验的物种中有41(64.1%)个物种表现了Janzen-Connell 假说的繁殖体对后代的距离制约效应。同时，54(84.4%)个物种的小树成为新的成年树，出现在成年体周围小于5m的距离内的比例最高。结果表明这个效应提高成年树的间距是有限的，然而，它仍然调节了样地内大部分物种的分布格局，促进了物种共存。 同种密度制约调节建成树木（胸径≥1cm）的空间结构得到很好的研究。然而最近的研究表明：病菌不仅在同种个体之间传播，同时也在近缘物种之间传播。因此，只包括同种个体的密度制约模型可能大大低估了密度制约效应的作用。本研究分析了古田山24 公顷内159 个物种。运用平均谱系多样性指数(APd) 和最近分类谱系多样性指数(NTPd)检验随着目标个体径级的增加系统发育结构变化的趋势。研究发现，在15、20、30m 的尺度上，APd 指数都随着生长阶段的增加而显著提高，在10、15、20、30m 的尺度上，NTPd 随着生长阶段的增加而显著提高；在5m 的尺度上，谱系多样性与生长阶段不存在显著关联性，这些结果表明谱系多样性制约与取样尺度相关。在DBH >30 cm 生长阶段， APd 下降，NTPd 上升，说明谱系多样性制约加大老树之间的谱系距离，但是由于类似的生境偏好，又倾向于聚集在类似的生境。 本研究的结果表明同种和近缘种的密度制约是亚热带常绿阔叶林生物多样性群落水平上重要的维持机制，为Janzen-Connell 假说提供了支持；同时，生境异质性和局部扩散能在维持森林物种多样性中发挥重要作用。

Exciton dynamics in self-organized InAs/GaAs quantum dots

Using a newly-developed population mixing technique we have studied the exciton dynamics in self-organized InAs/GaAs quantum dots (QDs). It is found that the exciton lifetime in self-organized InAs/GaAs QDs is around 1 ns, almost independent of InAs layer thickness. The temperature dependence of the exciton lifetime varies from sample to sample, but no obvious experimental evidence was found that the lifetime is related to the delta-function of density of states in QDs. We have also found that the population mixing technique can be used to directly reveal the band-filling effect in the excited states of the QDs.

Phase equilibria and plate-fluid interfacial tensions for associating hard sphere fluids confined in slit pores

The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.

黄土丘陵沟壑区退耕地土壤种子库对植被恢复的影响

为了探讨土壤种子库对植被恢复的影响,该文在野外调查和室内试验的基础上,采用典范变量分析,研究了黄土丘陵沟壑区退耕地土壤种子库密度、土壤水分和养分、地形因子以及退耕年限对植物群落变化的影响,量化了土壤种子库对植被恢复的贡献。结果表明:影响植物群落变化的因子有土壤水分、速效磷、土壤种子库和坡向;仅用土壤种子库只可解释植物群落变化的32.1%;由于退耕地土壤种子库的优势种主要为猪毛蒿,其植被恢复潜力与速度比较小。黄土丘陵沟壑区退耕地植被恢复需要适度的人为干预,有必要适当引进一些演替后期物种,如白羊草、铁杆蒿、长芒草等物种,以缩短演替时间,加速退耕地植被恢复进程,促进黄土丘陵沟壑区水土流失的防治。

厌氧好氧一体化生物反应器处理发酵废水的中试研究

一体化反应器由于投资少、占地小、管理运行方便等优点而备受青睐。但现有的一体化反应器大都适用于处理中低浓度废水，耐受负荷普遍偏低。本课题研制出新型高效的厌氧好氧一体化生物反应器，旨在通过反应器结构优化、高效微生物载体研制、配合高效微生物菌剂技术处理中高浓度有机废水，实现高效和低耗，降低设备造价，提高反应器运行稳定性。 首先开展了菌剂对废水的适配试验。采用15种不同的微生物菌剂，以葡萄糖配水、中药提取废水、啤酒废水、氨氮配水为基质，分别测定了微生物菌剂的耗氧速率和厌氧比产甲烷速率，以其为指标比较了各菌剂对废水的适配性。根据结果选择活性高的14＃、8＃、10＃菌剂，在试验室进行了菌剂对废水的连续处理试验，取得良好的处理效果，为菌剂在厌氧好氧一体化生物反应器的小试、中试中的应用奠定了基础。 经小试研究后，又对厌氧好氧一体化生物反应器进行了处理发酵废水的中试研究。试验结果表明，反应器启动快，系统有机负荷2.72 kgCODm-3d-1时整个反应器去除率保持在84.5％～93.19％，在30多天内一次启动成功。冲击负荷试验中，系统总有机负荷最高可达到8.88 kgCODm-3d-1，系统去除率稳定在88.10％～96.88%，说明反应器处理效率高，抗冲击能力强。稳定运行期间，COD去除率可达90％以上，各项指标都能达到国家排放标准。 此外，对反应器配套系统高效菌剂、高分子复合颗粒载体进行了研究。结果显示，菌剂与反应器适配良好，各功能区形成了丰富、高活性的微生物，厌氧区颗粒污泥TS高达83.9 gL-1，VS/TS为56.9％～57.4％，比产甲烷活性为280～350 mLCH4 gvss-1d-1；好氧区固定化微生物TS高达1.921 gL-1，VS/TS为94.02～94.30％。对载体性能的研究表明，此高分子复合颗粒载体密度适中，易于流化，不易流失；粗糙多空，易于挂膜；且无生物毒害作用，稳定安全，是一种优良的生物载体。反应器各功能区对废水的降解过程分析，说明了反应器、菌剂、载体适配良好，在其协同作用下，实现了污染物的高效降解。 The integrated reactors were popular because of their characteristics such as little investment, small occupation of land, convenient of manage and running etc. But the present integrated reactors were mostly applied for treating wastewater of low concentration, the load tolerance was generally on the low side. A new type integrated anaerobic-aerobic bio-reactor was developed, which was conducted to treating organic wastewater of middle or high concentration by optimization of reactor structure, development of efficient microbe carrier and adaptation of high active microbial blends, to achieve high efficiency and low consume, reduce equipment cost, enhance running stabilization of reactor. The adaptability test of microbial blends on different wastewater was carried on firstly. Oxygen consumption rate and anaerobic specific activity of methane producing of 15 different microbial blends were measured separately taking glucose artificial wastewater, Chinese herb extracting wastewater, brewery wastewater and ammonia nitrogen artificial wastewater as substrate, by which the adaptabilities of different microbial blends to wastewater were compared. According to the results high active microbial blends 14#, 8# and 10# were selected and used in the continuous treatment of wastewater in the laboratory and had obtained good effect, which had laid a foundation for application microbial blends to small scale test and pilot test of integrated anaerobic-aerobic bio-reactor. After the small scale test, the pilot test of the integrated anaerobic-aerobic bio-reactor treating fermentation wastewater was carried on. The test results showed fast initiation of the reactor. When system organic load reached 2.72 kgCODm-3d-1the COD removal rate of the reactor was stable between 84.5%～93.19% and it initiated successfully in more than 30 days at a time. In the load shock test the maximum organic load of system could reach to 8.88 kgCODm-3d-1 and the COD removal rate could be stable between 88.10%~96.88% which indicated that the reactor was efficient for treating wastewater and had strong resistance to shock load. At stable running period the COD removal rate of the reactor was over 90% and each index of wastewater could reach to the national discharge standards. In addition, the high active microbial blends and the macromolecule compound granule carrier, the matching system of the reactor was studied. It showed that the microbial blends adapted well to the reactor and abundant and high active microbes were formed in each functional field. The TS of granule sludge in anaerobic field was as high as 83.9 gL-1, the VS/TS was 56.9%~57.4%, the specific activity of methane producing was 280~350 mLCH4 gvss-1d-1. And the TS of immobilized biological granule was as high as 1.921 gL-1, the VS/TS was 94.02%~94.30%. Study on the carrier showed that the self-made macromolecular compound granule carrier was moderate of density, easy of fluidization, unease of running off, rough and porous, easy of films fixation, no bio-toxic, stable and safe, was a kind of superior carrier. Analysis of degradation process in each functional field confirmed the reactor, microbial blends and carriers were in good adaptation and wastewater was decontaminated by their cooperation.

Single particle properties in asymmetric nuclear matter and TBF rearrangement effect

We have developed the formula and the numerical code for calculating the rearrangement contribution to the single particle (s.p.) properties in asymmetric nuclear matter induced by three-body forces within the framework of the Brueckner theory extended to include a microscopic three-body force (TBF). We have investigated systematically the TBF-induced rearrangement effect on the s.p. properties and their isospin-behavior in neutron-rich nuclear medium. It is shown that the TBF induces a repulsive rearrangement contribution to the s.p. potential in nuclear medium. The repulsion of the TBF rearrangement contribution increases rapidly as a function of density and nucleon momentum. It reduces largely the attraction of the BHF s.p. potential and enhances strongly the momentum dependence of the s.p. potential at large densities and high-momenta. The TBF rearrangement effect on symmetry potential is to enhances its repulsion (attraction) on neutrons (protons) in dense asymmetric nuclear matter.

密度对刺槐幼苗生物量及异速生长模式的影响

刺槐(Robinia pseudoacacia)具有较强的生态适应性和抗逆能力,是黄土高原植被恢复和生态重建的主要优良树种之一(程积民等,2002;陈云明等,2002)。黄土高原地区刺槐人工林密度偏大,且多为低产林(余新晓等,1996;韩芯莲等,1996;2003)。王百田等(2005)认为黄土高原刺槐单木总生物量及各部分生物量都是密度的幂函数关系,但低密度林分和高密度林分的总生物量都比中间密度林分的总生物量高。种植密度不仅影响刺槐林地生物量,而且刺槐林地出现土壤干层的部分原因就是栽植密度过大(韩芯莲等,2003),其林地生产力的维持以及可持续生长成为林草植被建设中亟待解决的问题。植物密度对种群个体数量和生长的调控可以维持种群对资源的合理利用,保持种群的稳定性(Watkinson,1980)。因生长资源的强制分配,种植密度能引起植株个体间相互作用,密度增加导致植物种内竞争产生,使种群中单株生长量和生物量发生改变(李博等,2000)。竞争的实质是植物对地上光照和地下养分资源的利用,在共享资源有限的情况下竞争会导致植物个体生长量和存活率的降低(李博等,1998)。种内竞争对植物个体生长的影响,与植物“自疏法则”的...