Applicability of medium-size basis sets in calculations of molecular dynamic polarisabilities

Static and dynamic average polarisabilities and polarisability anisotropies of seven linear non-polar and polar molecules are calculated within the CCS, CC2, and CC3 approximations using a range of medium-sized basis sets: the polarised LPol-n (n = ds, dl, fs, fl), the aug-pc-n (n = 1, 2), the def2-SVPD, and -TZVPD basis sets. Reference values are obtained using a hierarchy of Dunning's (d-)aug-cc-pVXZ (X = D, T, Q, 5) basis sets. The results are discussed together with the available CCSD values in terms of basis set and correlation method errors, and their ratio. Detailed analysis shows that already the def2-SVPD basis set can be used in CCS polarisability calculations. When affordable, the slightly larger aug-pc-1 basis set is recommended, as it leads to significant reduction of basis set error. The def2-TZVPD, LPol-ds, and aug-pc-2 basis sets are optimal choice within the CC2 approximation, with the latter allowing to approach the CC2 basis set limit. The LPol-ds, -dl, and def2-TZVPD sets outperform the aug-cc-pVTZ set in average polarisability CCSD calculations, with the def2-TZVPD being competitive to other reduced-size sets also in determination of polarisability anisotropy. The aug-pc-2 basis is a particularly attractive choice for CCSD, giving the accuracy of aug-cc-pVQZ at a significantly reduced computational cost. The polarisability anisotropy is shown to be more computationally demanding than the average polarisability, in particular with respect to the accuracy of the correlation method and an accurate evaluation of this property requires at least the CCSD model.     

Ugi three-component coupling reaction for the synthesis of 2-(6-oxo-11-phenyl-7,8-dihydrobenzo[b]pyrrolo[1,2-d][1,4]diazocin-5(6H)-yl)-2-phenylacetamide derivatives

A three-component, four center Ugi reaction of 3-(1-(2-aminophenyl)-5-phenyl-1H-pyrrol-2-yl)propanoic acid with aromatic aldehyde and t-butyl isocyanide has been achieved to produce a novel class of N-tert-butyl-2-(6-oxo-11-phenyl-7,8-dihydrobenzo[b]pyrrolo[1,2-d][1,4]diazacine-5(6H)-yl)-2-phenylacetamides in moderate to good yields.     

Structure and stability of X4Y4H4 (XY=CC,BN)

Ab initio calculations have been carried out to study the structures and relative stabilities of the planar eight‐membered ring B₄N₄H₄ and its isoelectronic species C₈H₄ at the HF/6‐31G*, MP2/6‐31G*, MP2/6‐311G**, and MP4SDQ/6‐31G* levels. The analyses of Milliken population, vibration frequencies, π‐molecular orbital components, and orbital energy levels were used to evaluate the relative stabilities of these two similar systems. The homodesmotic reactions were also taken to be a useful index of relative stability for X₄Y₄H₄ (XY=CC, BN) and gave the resonance energies with MP4SDQ/6‐31G* of C₈H₄ (?37.2 kcal/mol) < B₄N₄H₄ (?29.2 kcal/mol). Furthermore, we calculated the thermodynamic functions of these reactions to discuss the influence of temperature. It is concluded that B₄N₄H₄ may exist in theory and could be a little more stable than C₈H₄. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 293–298, 2001     

光电倍增管在磷酸液声致发光实验中的应用

对不同厚度液体进行光强测量,深入探索空化气泡的运动,研究发光机理很有意义。用超声激励法在磷酸液体中实现多泡声致发光,研究不同共振频率下发光的特点。利用光电倍增管多次测量发光强度相互比较,结果是在液体厚度10 cm、驱动频率f=21.061kHz和f=20.316kHz时,周期性较好为50μs,液体通过漩涡集中气泡可以使更多气泡发光;在液体厚度3 mm、驱动频率f=17.91kHz和f=19kHz时,周期性很好为25μs;且光信号都较强。结论是磷酸中声致发光强度、周期与液体厚度、驱动频率密切相关。本文以磷酸液多泡声致发光实验研究为基础,从内部和外部原理来出发,详细介绍了光电倍增管在多泡声致发光光强测量中的实用,为今后研究者提供了一些经验。根据实验过程中遇到的一些实际问题提出了建议和改善意见。     

Design of highly active heterogeneous palladium catalysts for the activation of aryl chlorides in Heck reactions

In situ generation of highly active palladium species by intermediate dissolution of Pd from solid supported catalysts has been demonstrated to be a very successful approach for the activation of aryl chlorides in Heck reactions. The new ‘heterogeneous’ Pd catalysts act as reservoir for molecular Pd species with unsaturated coordination sphere in solution. Crucial Pd leaching and re-deposition onto the support can be controlled by optimization of reaction conditions and by the properties of the catalysts. Pd is re-deposited onto the support at the end of the reaction. The catalysts, palladium supported on activated carbon, on various metal oxides or fluorides and Pd complexes in zeolites, are easy to prepare, though the preparation conditions are crucial. The catalysts convert all aryl bromides completely within minutes (TON 100,000). Aryl chlorides (even deactivated ones) are converted with high yields, within 2-6 h. The catalysts belong to the most active ones in Heck reactions at all (including best homogeneous systems) and fulfill all relevant requirements for practical applications in laboratory and industry.     

Concentration quenching of fluorescence from the (P0 + P1) manifold in heavily-doped Pr: ZBAN glasses

Fluorescence waveforms from the (³P₀ + ³P₁) manifold in Pr³⁺ doped ZBAN glass at wavelengths of 520, 635 and 695 nm were measured for Pr³⁺ concentrations from 4 to 12 mol%. The waveforms were found to be non-exponential with decay rates rapidly increasing with Pr³⁺ concentration and independent of whether the ³P₀ or the ³P₁ level was excited. The multipolar energy transfer model was used to analyse the waveforms and this showed that concentration quenching was due to cross-relaxation by dipole-dipole interaction. The critical concentration, at which the cross-relaxation rate equals the intrinsic decay rate, was found to be of 2.06 × 10²⁶ m⁻³ (1.20 mol%). There was no evidence of excitation diffusion for Pr³⁺ concentrations of up to 12 mol%.     

Enhanced frequency upconversion in Er doped fluoroindate glass due to energy transfer from Tm

Energy transfer processes between Er³⁺ and Tm³⁺ were investigated examining the frequency upconversion emissions in a fluoroindate glass pumped at 790 nm. A 60-fold enhancement in the emission at ≈670 nm originating from Er³⁺ was observed when Tm³⁺ at concentration of 2% was introduced in a sample containing 2% of Er³⁺. The results are explained considering the influence of cross-relaxation processes between the active ions.     

云环境下景区游客流量监控与推荐系统设计

设计了云环境下景区游客流量监控与推荐系统,包括CC3200流量监控与景点推荐两部分,流量监控由RFID电子门票统计游客数量,数据经Wi-Fi上行本地AP节点,由AP节点汇聚至云推荐服务器;当前游客流量、时间富裕度、游客满意度,经服务器解析计算得景点综合推荐指数,主动为游客推荐旅游景点,规划最佳游览路线。经测试,系统工作稳定、数据准确,适用于各类景区游客流量监控与推荐服务。     

A MINI MULTI-GAS DETECTION SYSTEM BASED ON INFRARED PRINCIPLE

To counter the problems of gas accidents in coal mines, family safety resulted from using gas, a new infrared detection system with integration and miniaturization has been developed. The infrared detection optics principle used in developing this system is mainly analyzed. The idea that multi gas detection is introduced and guided through analyzing single gas detection is got across. Through researching the design of cell structure, the cell with integration and miniaturization has been devised. The way of data transmission on Controller Area Network (CAN) bus is explained. By taking Single-Chip Microcomputer (SCM) as intelligence handling, the functional block diagram of gas detection system is designed with its hardware and software system analyzed and devised. This system designed has reached the technology requirement of lower power consumption, mini-volume, big measure range, and able to realize multi-gas detection.