Non‐empirical calculations of NMR indirect carbon–carbon coupling constants. Part 4: Bicycloalkanes

A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd.     

Ultraslow phonon-assisted collapse of tubular image states

We predict ultraslow collapse of “tubular image states” (TIS) on material surfaces. TIS are bound Rydberg-like electronic states formed at large distances (∼30 nm) from the surfaces of suspended circularly-symmetric nanowires, such as metallic C nanotubes. The states are formed in potential wells, resulting from a combination of the TIS-electron attraction to image charges in the nanotube and its centrifugal repulsion, caused by spinning around the tube. We demonstrate that TIS can collapse on the tube surface by passing their angular momentum l to circularly polarized flexural phonons excited in the tube. Our analysis shows that for highly detached TIS with l ? 6 the relaxation lifetimes are of the order of 10 ns-1 μs, while for l < 6 these lifetimes are reduced by several orders of magnitude.     

一种外置式视频同步信号发生器的设计

对随机视频信号的特点进行了研究，提出了采用谱分析提取随机视频信号的同步频率的方法，根据数据传输的要求设计了基于USB接口的外置式视频同步信号发生器并给出了系统的硬件框图和软件流程。系统具有自动分析随机视频信息隐含的同步信号频率，精确产生同步脉冲信号的特点，满足随机视频信号采集和稳定显示的同步要求。同步精度达到300帧内图像漂移小于1个像素。利用该视频同步信号发生器控制非标准图像采集卡实现了计算机辐射的随机视频信号的采集和稳定显示。     

基于滑窗结构的软输出维特比算法的实现

文章在对软输出维特比算法(SOVA)进行推导的基础上，分析了软信息的提取过程。同时从硬件实现的角度考虑，提出了一种基于滑动窗1：3结构的SOVA算法实现方案，该算法大大降低了算法实现复杂度和译码延迟，同时通过调整滑窗参数，可以取得与非滑窗SOVA算法几乎相同的性能。     

Structure and Structural Nonrigidity of Tetrachlorodibenzo-p-Dioxin Radical Cations

Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD.     

世界各国(或地区)推进RFID的策略

介绍了一些国家和地区发展RFID的政策和推进措施，总结了各国发展RFID的共性。     

基于SDL的通信软件维护模型SMM

软件维护是软件生存周期的一个重要且花费很大的阶段，维护工作的自动化是软件行业十分迫切的需要。本文提出了一个基于ＩＴＵ－ＴＳＤＬ语言的通信软件维护模型ＳＭＭ。在此模型中，软件维护被分成三个部分：建立面向维护的数据库，制定维护规范和基于功能转换的自动维护。该模型将有助于软件维护支撑环境的建立     

计算机辅助电子线路实验的思考与探索

本文介绍了EltctronicWorkbench软件和计算机虚拟仪器系统，采用计算机模拟仿真技术对电子线路实验加以辅助设计和探索。     

Assignment of conformation-sensitive near-infrared bands in high-spin ferrous haemoproteins. Low-temperature magnetic circular dichroism data

An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD) spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand (i.e. myoglobin, haemoglobin and horseradish peroxidase). Received: 4 February 1997 / Accepted: 1 May 1997     

自发参量下转换制备双光子纠缠态在量子信息学中的应用

叙述了自发参量下转换制备双光子纠缠态技术的发展历程、技术原理以及在量子信息学中的应用，并介绍了国内这一领域的进展。