Developing the Low-Temperature Oxidation Mechanism of Cyclopentane: An Experimental and Theoretical Study

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.     

A possibility of parallel and anti-parallel diffraction measurements on neutron diffractometer employing bent perfect crystal monochromator at the monochromatic focusing condition

In a conventional diffractometer having single monochromator, only one position, parallel position, is used for the diffraction experiment (i.e. detection) because the resolution property of the other one, anti-parallel position, is very poor. However, a bent perfect crystal (BPC) monochromator at monochromatic focusing condition can provide a quite flat and equal resolution property at both parallel and anti-parallel positions and thus one can have a chance to use both sides for the diffraction experiment. From the data of the FWHM and the Δd/d measured on three diffraction geometries (symmetric, asymmetric compression and asymmetric expansion), we can conclude that the simultaneous diffraction measurement in both parallel and anti-parallel positions can be achieved.     

Establishment of Illuminance Scale at UME with an Accurately Calibrated Radiometer

Traceability in illuminance measurements at the National Metrology Institute of Turkey (TüBITAK-UME) was established in 2003 with a detector-based realization. The new measurement technique was developed for the determination of illuminance responsivity and upgrating of the illuminance scale. The unit of the illuminance responsivity, in A/lx, was measured with an expanded uncertainty of 0.2% (k = 2) by supplying using the developed scanning technique for the calculation of color correction factor. The surface of a radiometer was scanned using a double-monochromator facility upgraded with an x-y scanning system. The illuminance responsivity as a function of bandpass and temperature were also investigated in this study. To use a radiometer in the photometric applications of metrology, a light-sensitive device, a so-called trap detector, was characterized by measuring the absolute responsivity, the non-linearity, and spatial non-uniformity.     

VUV-UV excited luminescent properties of LnCa4O(BO3)3:RE (Ln=Y, La, Gd; Re=Eu, Tb, Dy, Ce)

Calcium lanthanide oxyborate doped with rare-earth ions LnCa₄O(BO₃)₃:RE³⁺ (LnCOB:RE, Ln=Y, La, Gd, RE=Eu, Tb, Dy, Ce) was synthesized by the method of solid-state reaction at high temperature. Their fluorescent spectra were measured from vacuum ultraviolet (VUV) to visible region at room temperature. Their excitation spectra all have a broadband center at about 188 nm, which is ascribed to host absorption. Using Dorenbos’ and Jφrgensen's work [P. Dorenbos, J. Lumin. 91 (2000) 91, R. Resfeld, C.K. Jφrgensen, Lasers and Excite States of Rare Earth [M], Springer, Berlin, 1977, p. 45], the position of the lowest 5d levels E(Ln,A) and charge transfer band E_ct were calculated and compared with their excitation spectra.Eu³⁺ and Tb³⁺ ions doped into LnCOB show efficient luminescence under VUV and UV irradiation. In this system, Ce³⁺ ions do not show efficient luminescence and quench the luminescence of Tb³⁺ ions when Tb³⁺ and Ce³⁺ ions are co-doped into LnCOB. GdCOB doped with Dy³⁺ shows yellowish white light under irradiation of 254 nm light for the reason that Gd³⁺ ions transfer the energy from itself to Dy³⁺. Because of the existence of Gd³⁺, the samples of GdCOB:RE³⁺ show higher excitation efficiency than LaCOB:RE³⁺ and YCOB:RE³⁺, around 188 nm, which indicates that the Gd³⁺ ions have an effect on the host absorption and can transfer the excitation energy to the luminescent center such as Tb³⁺, Dy³⁺ and Eu³⁺.     

TiVI真空紫外光谱

用1m法向入射光谱仪观察三电极真空火花发射的Ti五次离化光谱。在24～200nm波段内观察到157条TiVI的新谱线。根据新归属的TiVI谱线定出11个新能级,并对5个有疑问的能级值作了修正。     

双晶单色器弧矢聚焦晶体面形有限元分析

简要介绍了弧矢聚焦双晶单色器的基本原理、聚焦晶体的压弯以及鞍形形变的抑制,提出了柔性铰链弧矢聚焦晶体压弯机构,对弧矢聚焦晶体衍射面的子午形变和弧矢弯曲面形进行了有限元分析;用光学追踪程序SHADOW得出了弧矢聚焦晶体衍射面面形对单色器的光通量和分辨率的影响。     

La2CaB10O19∶Ce3+在VUV-Vis范围的发光性质研究

通过研究La2CaB10O19∶Ce3+在VUV-Vis范围的光谱, 发现Ce3+在La2CaB10O19中共有两种格位, 分别取代了十配位的La3+和八配位的Ca2+, 从而发射光谱中没有出现特征的双峰, 而出现了峰值约位于307, 330和356 nm的3个发射峰.由于在低对称性晶体场中d轨道的分裂, 激发光谱中位于194, 224, 243, 260, 274和318 nm的峰是由两个格位的Ce3+的f-d跃迁引起的.Ce3+占据两个格位, 可以通过以Eu3+为荧光探针的发射光谱中出现的两个5D0-7F0跃迁得到验证.峰值位于162 nm的激发谱带是基质吸收带, 与基质禁带宽度相对应.通过计算, 不排除其中包含O2-→Ce3+的电荷迁移带的可能性.     

Quantum chemical modeling for 157 nm photolithography

In its continuing quest for smaller length scales, the electronics industry plans to introduce 157 nm as the next lithographic wavelength. Accordingly, there is a pressing need to develop photoresists that are more transparent, and pellicles that are both more transparent and more durable. With the advent and popularization of time-dependent density functional theory (TD-DFT), we now have a practical quantum chemical method for calculating excitation energies and transition moments in the vacuum ultraviolet (VUV) which can greatly assist in the scouting of highly transparent materials. We have performed TD-DFT calculations for a broad variety of fluorinated molecules and we will report calculated VUV photoabsorption spectra for a large family of model fluorohexanes. These calculations, which span a range from 1-fluorohexane to CH₃CF₂CF₂CF₂CF₂CH₃, illustrate some of the principles one may use to design low absorption polymeric materials.     

Vacuum Ultraviolet Photolysis of Polyethylene,Polypropylene, and Polystyrene

Using infrared reflection absorption spectroscopy (IRRAS), quartz crystal microbalance (QMB) measurements, and X-ray photoelectron spectroscopy (XPS) in combination with chemical derivatization techniques the VUV photolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated. A mass balance obtained from the quantification of the data was used to suggest reaction path ways. Although PE and PP behave similar, the mass loss is about 8 times higher in the case of PP. These differences originate from the higher disproportionation to recombination ratio for the branched polymer. Both polymers form double bonds and at extended treatment times they tend to crosslink. PS is rather stable due to the possibility of the energy dissipation by fluorescence.     

共沉淀法合成稀土正磷酸盐(La,Gd)PO4:RE3+(RE=Eu,Tb)及其真空紫外光谱特性

采用共沉淀法制备了稀土正磷酸盐荧光粉(La,Gd)PO4:RE3+(RE=Eu,Tb).红外光谱分析发现GdPO4的红外光谱吸收峰与LaPO4一致,只是峰位向高波数方向移动.(La,Gd)PO4:RE3+的真空紫外光谱特性研究表明,Gd3+在能量传递过程中起中间体作用.XPS研究揭示,LaPO4的价带由O2-的2p能级构成,而GdPO4的价带则是由O2-的2p能级和Gd3+的4f能级共同构成.