Synthesis and characterization of poly(ethylene glycol) bottlebrush networks via ring-opening metathesis polymerization

Herein it is reported how the overlap concentration (C*) can be used to overcome crosslinking due to diol impurities in commercial poly(ethylene glycol) (PEG), allowing for the synthesize of bottlebrush polymers with good control over molecular weight. Additionally, PEG-based bottlebrush networks are synthesized via ring-opening metathesis polymerization, attaining high conversions with minimal sol fractions (<2%). The crystallinity and mechanical properties of these networks are then further altered by solvent swelling with phosphate buffer solution and 1-ethyl-3-methylimidazolium ethyl sulfate/dichloromethane cosolvents. The syntheses reported here highlight the potential of the bottlebrush network architecture for use in the rational design of new materials.     

周向重叠三分螺旋折流板换热器壳侧性能试验研究

对倾斜角为20°、24°、28°和32°的单头以及32°的双头周向重叠三分螺旋折流板换热器和弓形折流板换热器的传热和压降性能进行了测试,换热器采用公共壳体和可更换管芯结构。采用壳侧轴向雷诺数和轴向欧拉数分别作为反映壳侧流量和阻力系数的无因次参数。试验结果显示在试验范围内周向重叠三分螺旋折流板换热器壳侧换热系数、壳侧压降和综合性能指标都随着倾斜角增大而减小;倾斜角20°方案的性能指标最佳,其平均壳侧努塞尔数和轴向欧拉数与弓形折流板方案的数值之比分别为1.123和0.45;双头螺旋折流板方案的换热系数和压降都大于同样倾斜角的单头螺旋折流板方案,但两者的综合性能较接近。     

C-H 键和C-C 键核自旋偶合常数的理论研究

利用PM3级别最大重迭对称性分子轨道法和最大键级杂化轨道方法,计算了系列烃类化合物的杂化轨道和电荷分布,拟合出计算C-H及C-C偶合常数的简单关系式. 研究了各种烃类分子中不同的C-H键和C-C键偶合常数,理论计算值和实验数据都较为符合. 进一步验证了直接键连¹J_CX偶合常数主要取决于偶合作用中的Fermi接触项,为从简单价键理论角度解释和计算¹J_CH和¹J_CC提供了一种简便直观的方法.     

Suppression of Anti-resonant Effect in Presence of Band Overlap

By exact resolution of coupled ideal chains connecting an extra side site, we show that the so-called ＂anti-resonant effect＂ is suppressed when the electron energy is inside the overlap region of extended bands of the ideal tight-binding chains. When the electronic energy is outside the band overlap region, the existence of ＂anti-resonant effect＂ is tuned by details of local connectivity around the extra side site and can be suppressed by introduction of magnetic flux.     

The 193 nm photolysis of NO2: NO(ν) vibrational distribution,O(1D) quantum yield and emission from vibrationally excited NO2

Time resolved Fourier transform infrared emission has been used to study the photolysis of NO2 and its dimer N2O4 at 193 nm. NO(ν) populations from the photolysis of NO2 show a bimodal distribution, peaking at ν = 5 and with a subsidiary maximum at ν = 14, close to the energetically allowed limit. The results are discussed in terms of previous measurements near this photolysis wavelength of the kinetic energies of the two possible O atomic fragments, O(3P) and O(1D), and on the electronic states of the parent molecule which can be populated. The O(1D) yield has been measured as 0.51 ± 0.04, in good agreement with previously reported values. Emission from vibrationally excited NO2 arises from the dissociation of N2O4 and is similar to that observed from photolysis at 248 nm.     

On the Calculation of Two-Center Overlap Integrals with STO's Using Zeta-Function Method and Multipole Moments

One electron two-center overlap integrals are re-derived using Barnett's -function method and Guseinov electric-multipole-moments translation technique. To evaluate these integrals a computer program has been constructed. The obtained results are in good agreement with literature.     

On Evaluation of Overlap Integrals with Noninteger Principal Quantum Numbers

By use of complete orthonormal sets of ψ^α exponential-type orbitals (ψ^α-ETOs,α=1,0,-1,-2,...) the series expansion formulas for the noninteger n Slater-type orbitals (NISTOs) in terms of integer n Slater-type orbitals (ISTOs) are derived. These formulas enable us to express the overlap integrals with NISTOs through the overlap integrals over ISTOs with the same and different screening constants. By calculating concrete cases the convergence of the series for arbitrary values of noninteger principal quantum numbers and screening constants of NISTOs and internuclear distances is tested. The accuracy of the results is quite high for quantum numbers, screening constants and location of STOs.     

偏振态对飞秒激光加工石英玻璃表面质量的影响

为研究线偏振和圆偏振对飞秒激光烧蚀加工石英玻璃表面质量的影响,开展不同扫描速度的线烧蚀试验和不同线重叠率的面烧蚀试验。研究了线、圆偏振光对烧蚀线宽度的影响,利用光学显微镜和环境扫描电子显微镜观察烧蚀形貌,并使用三维表面轮廓仪进行烧蚀面粗糙度分析。结果表明:线偏振光烧蚀线宽度大于圆偏振光,且激光功率越大,线宽差异越明显;当线重叠率在65%~90%时,线偏振光烧蚀表面粗糙度随重叠率增大而增大,在重叠率为65%时达到1.33μm;线轮廓算术平均偏差随重叠率增大先减小后增大,并在重叠率为80%时达到较小值1.05μm;当重叠率不到80%时,线偏振光烧蚀面线轮廓算术平均偏差比圆偏振光小;重叠率为90%时,其线轮廓算术平均偏差反而比圆偏振光大。     

S2O‾自由基光电子能谱的Franck-Condon分析

本文考虑多振动模混合和热带效应,凭借谐振子模型,推得计算两维-四振动模Franck-Condon重叠积分的解析表示,且应用于S2O‾ 自由基光电子能谱的理论研究。对于S2O( 1A′) – S2O‾( 2A″) 光脱附过程,结合分子轨道从头算和密度泛函理论,计算Franck-Condon因子,从而得到电子跃迁振动谱线的相对强度,理论上得到的光电子能谱与实验上观测到的能谱达到较好的一致;进一步在光谱模拟过程中,拟合实验能谱得到可靠的负离子自由基S2O‾电子态（ 2A″）的几何结构参数：键长R(SS) = 2.008 +/-0.005Å 和 R(SO) = 1.519+/-0.005Å.     

An atomic linear Stark shift violating P but not T arising from the electroweak nuclear anapole moment

We propose a direct method of detection of the nuclear anapole moment. It is based on the existence of a linear Stark shift for alkali atoms in their ground state perturbed by a quadrupolar interaction of uniaxial symmetry around a direction and a magnetic field. This shift is characterized by the T-even pseudoscalar ( ^. )(∧ ^. )/B ². It involves on the one hand the anisotropy of the hyperfine interaction induced by the quadrupolar interaction and, on the other, the static electric dipole moment arising from electroweak interactions inside the nucleus. The case of ground state Cs atoms trapped in a uniaxial (hcp) phase of solid ⁴He is examined. From an explicit evaluation of both the hyperfine structure anisotropy and the static dipole deduced from recent empirical data about the Cs nuclear anapole moment, we predict the Stark shift. It is three times the experimental upper bound to be set on the T-odd Stark shift of free Cs atoms in order to improve the present limit on the electron EDM. Received 20 December 2000