Quadrupolar Ultrafast Charge Transfer in Diaminoazobenzene-Bridged Perylenediimide Triads

Strong push-pull interactions between electron donor, diaminoazobenzene (azo), and an electron acceptor, perylenediimide (PDI), entities in the newly synthesized A−D−A type triads (A=electron acceptor and D=electron donor) and the corresponding A−D dyads are shown to reveal wide-band absorption covering the entire visible spectrum. Electrochemical studies revealed the facile reduction of PDI and relatively easier oxidation of diaminoazobenzene in the dyads and triads. Charge transfer reversal using fluorescence-spectroelectrochemistry wherein the PDI fluorescence recovery upon one-electron oxidation, deterring the charge-transfer interactions, was possible to accomplish. The charge transfer state density difference and the frontier orbitals from the DFT calculations established the electron-deficient PDI to be an electron acceptor and diaminoazobenzene to be an electron donor resulting in energetically closely positioned PDI ^δ− -Azo ^δ+ -PDI ^δ− quadrupolar charge-transfer states in the case of triads and Azo ^δ+ -PDI ^δ− dipolar charge-transfer states in the case of dyads. Subsequent femtosecond transient absorption spectral studies unequivocally proved the occurrence of excited-state charge transfer in these dyads and triads in benzonitrile wherein the calculated forward charge transfer rate constants, k_f, were limited to instrument response factor, meaning >10¹² s⁻¹ revealing the occurrence of ultrafast photo-events. The charge recombination rate constant, k_r, was found to depend on the type of donor-acceptor conjugates, that is, it was possible to establish faster k_r in the case of triads (∼10¹¹ s⁻¹) compared to dyads (∼10¹⁰ s⁻¹). Modulating both ground and excited-state properties of PDI with the help of strong quadrupolar and dipolar charge transfer and witnessing ultrafast charge transfer events in the studied triads and dyads is borne out from the present study.     

高精度单晶硅挠性摆式加速度计组件的工程化实现

针对单晶硅挠性摆式加速度计的高精度工程化应用需求,设计了加速度计组件及温控系统。针对大多数温控系统工作时的瞬时电流较大问题,设计了一种带抽头的加热片,将温控分为粗温控和精温控两个阶段,不同阶段采用不同的加热电阻。测试结果表明,设定目标温度为60℃,当外界环境温度从5℃到55℃变化时,温控系统到温时间小于15 min,控温精度小于±0.1℃,精温控时的最大电流为粗温控时的33.4%。连续15天通电实验表明,该组件的加速度计刻度系数K1稳定性小于10×10~(-6),偏值K0稳定性小于10μg,满足各类高精度、工程化的应用需求。     

Photoinduced Intramolecular Charge Transfer in Donor-acceptor Dyad and Donor-bridge-acceptor Triad

在fullerene-PBTDP-TPA三体体系中的光诱导的分子内电荷转移的实验基础上,分别利用密度泛函理论和含时密度泛函理论以及结合二维、三维实空分析方法对fullerene、PBTDP-TPA二体以及fullerene-PBTDP-TPA三体的基态和激发态的性质进行了理论研究．二维定点表象揭示了激发情况下电子和空穴的相干情况．三维跃迁矩阵展示了跃迁偶极矩的方向和强度,而且三维电荷差密度给出了光诱导的分子内电荷转移的方向和结果．同时,用二维和三维表象的方法对fullerene-PBTDP-TPA三体中光诱导的分子内电荷转移过程进行了验证,揭示了在给予者-桥-接收者三体分子体系中分子内激发时电荷转移的机制．除此之外,还发现直接从给予者到接收者超交换的分子内电荷转移极大地促进了给予者-桥-接收者三体分子体系内的电荷转移．     

The eight first vibrational states of the water molecule: measurements and analysis

In this work the spectrum of the water molecule has been the subject of extensive experimental and theoretical investigations. More than 1500 transitions have been assigned in a far infrared emission spectrum recorded in the 50-500 cm⁻¹ region and experimental rotational energies have been obtained for the second triad of interacting states, (0 3 0), (1 1 0), and (0 1 1), up to J=10 using flame spectroscopy. These new data along with a large data set of already published experimental rotational energies, high-resolution infrared transitions, and microwave lines, involving the eight first vibrational states, have been analyzed using the theoretical formalism developed for water in a previous paper (J. Mol. Spectrosc. 206 (2001) 83), which accounts for the anomalous centrifugal distortion as well as for the Fermi- and Coriolis-type couplings.     

对－氯苯乙烯和丙烯酸甲酯梯度共聚物的微观结构表征

对由原子转移自由基聚合(ATRP)方法得到的具有“活性”聚合特征的对－氯苯乙烯(S)和丙烯酸甲酯(M)梯度共聚物结构进行了表征．通过¹H、¹³C 核磁共振(NMR)方法和对羰基¹³C峰峰面积的拟合积分研究了该共聚物的单体以及以M为中心的三元组序列结构的组成含量随转化率的变化．研究结果表明：共聚物链中S和M单体含量随着转化率的增加分别表现出减小和增大的变化趋势;三元组序列结构的含量变化中,SMS和MMM分别呈现出单调下降和上升的变化,而MM/MMS则随着转化率的增加达到一个最大值,然后呈现下降趋势．本文还尝试运用了以M为中心的五元组序列结构对羰基¹³C峰峰面积进行更精确的拟合积分,其拟合峰面积的计算结果显示了与上述三元组序列结果相同的变化规律．     

New equation for calculating total interaction energy in one noncyclic ABC triad and new insights into cooperativity of noncovalent bonds

In this work, a new equation consist of A???B, B???C, A???BC, and AB???C interactions is proposed for calculating the total interaction energy of noncyclic ABC triads. New equations are also proposed for calculating the changes in values of A???B and B???C interactions on the formation of triad from the corresponding dyads. The advantages of equations proposed here in comparison with many‐body interaction energy approach are discussed. All proposed equations were tested in F₃MLi???NCH???HLH and F₃MLi???HLH???HCN (M = C, Si; L = Be, Mg) as well as H₃N???XY???HF (X, Y = F, Cl, Br) noncyclic A???B???C triads. The data show that the total cooperativity of triad correlates well with the sum of the changes in values of A???B and B???C interactions calculated through new equations proposed here. © 2016 Wiley Periodicals, Inc.     

槽道湍流近壁区相干结构的数值模拟

从流动稳定性理论中的共振三波出发，采用类似湍流直接数值模拟中的最小单元概念，用伪谱方法，对槽道湍流近壁区的单个相干结构进行了数值模拟，得到了与实验基本一致的结果，同时也搞清楚了在谱方法中用Ｃｈｅｂｙｓｈｅｖ－τ方法和配置点法哪个更精确的问题。     

On nonlinear oscillations of a thin bar

Summary Based on one of the simplest mathematical model of a solid, nonlinear interactions between waves in a rectilinear bar are investigated, in order to reveal and display a number of dynamic properties inherent not only to the bar, but also to most weakly nonlinear mechanical systems with internal resonances. The presence of internal resonances in the bar is twofold. Firstly, there exists a slow periodic energy exchange between the longitudinal and the two quasi-harmonic bending waves involved in the resonant triad due to the phase matching, secondly, triple-frequency envelope solitons can be created from the resonant triad with the same modal state. The paper investigates the evolution of waves in the bar with the aim to classify the elementary type of wave triplet resonant interactions and define their existence and coesistence areas.The research described here has been made possible in part by Grant N R9B000 from the International Science Foundation. The authors would like to thank Professor G.A. Maugin for having sent copies of his papers, in particular [23], as well as for his permanent interest in our work.     

Estimating Reactivity Ratios From Triad Fraction Data

Reactivity ratio estimation is a non-linear estimation problem. Typically, reactivity ratios are estimated using the instantaneous copolymer composition equation, otherwise known as the Mayo-Lewis model, based on low conversion (<5%) copolymer composition data. However, there are other instantaneous models, which can be used to estimate reactivity ratios, such as the instantaneous triad fraction equations. The aim of this paper is to determine the potential improvement in reactivity ratio estimates when triad fraction data is used in place of and in combination with copolymer composition data. The interest in using triad fraction data in parameter estimation, stems from the fact that there are a greater number of responses measured (six triad fractions) compared to composition leading to data with theoretically more information content. In principle this should lead to reactivity ratio estimates having less uncertainty. In this study, the parameter estimates are obtained by employing the error in variables model (EVM), assuming a multiplicative error structure. Several case studies involving published literature data for different copolymer systems are presented. As the case studies demonstrate in general more precise estimates can be obtained from triad fraction data. Combining the triad fraction with composition data leads to little additional improvement. However, discrepancies arise between reactivity ratios estimated from composition data compared with those obtained from triad fraction data depending upon the copolymer system. Those copolymer systems exhibiting more heterogeneity due to phase separation during polymerization may be showing more discrepancy.