线性响应和两种态特定方法模拟AF350电子跃迁的溶剂效应

在极化连续模型框架下比较了线性响应与两种不同态特定方法计算的溶液中Alexa Fluor 350(AF350)分子激发能和光谱移动值的差异. AF350的第一激发态S0→S1电子跃迁属于π→π^*跃迁, 主要对应于最高占据分子轨道(HOMO)到最低空轨道(LUMO)的跃迁. 该分子激发态偶极矩大于基态偶极矩, 激发态时溶质溶剂相互作用比基态时更强, 随着溶剂极性增大, 会发生光谱红移的现象. 与实验值相比, 线性响应和两种态特定方法均高估了激发能, 其中以IBSF(Improta-Barone-Scalmani-Frisch)方法得到的激发能最小, 矫正的基态反应场方法(cGSRF)得到的激发能最大. 对于光谱移动值, 3种方法与实验值相比都偏小, 线性响应方法(LR)计算出的误差最大, 而IBSF方法得到的结果与实验值最吻合, 是预测溶液中AF350分子激发能和光谱移动值最准确的方法. 对比了Marcus传统理论和基于约束平衡的非平衡溶剂化理论的结果, 发现后者得到的激发能和光谱移动值更接近于实验值.     

TiO_2纳米阵列光阳极光电催化水分解研究进展

光电催化水分解制氢是目前解决能源危机与环境污染最理想的技术之一.设计和构筑高效的光阳极是实现光电催化技术实际应用的关键.在众多半导体光阳极材料中,TiO_2纳米阵列由于其快的电荷传输速率,高的光热稳定性,无毒和成本低等优点,已经被广泛用于光电催化水分解反应的研究.但是TiO_2本征的光吸收范围窄、光生电荷复合率高、表面水氧化动力学缓慢严重地制约了其太阳能-氢能转换效率.我们结合近年来国内外及本课题组的研究工作详细论述了TiO_2纳米阵列的改性策略,主要包括利用元素掺杂来拓展TiO_2的光吸收范围并提高导电性,构筑异质结促进光电极电荷的分离与转移,半导体敏化增加光电极的可见光吸收并促进电荷转移,表面处理用于增加表面水氧化反应速率.最后指出了该材料发展现状,并对其发展前景做出展望.我们为进一步提高TiO_2纳米阵列的光电催化水分解活性提供了理论指导和实践借鉴.     

Advances in theoretical study on transition-metal-catalyzed C−H activation

Transition-metal-catalyzed C–H activation represents one of most attractive research fields in modern organic chemistry while theoretical studies have become a popular and effective tool for elucidating mechanism nowadays. The recent achievements in the cross field of the two orientations are reviewed in this article. The first part introduced the advances in theoretical study on transition-metal-catalyzed C–H activation. The elegant work reported mainly in and after 2013, classified according to the mechanisms of C–H activation, were covered. The second part provided an analysis on the distribution of quantum-chemical methods, solvation models and basis sets in the collected theoretical studies.     

Accelerated Curing Speed of Ethyl α‐Cyanoacrylate by Polymer with Catecholamine Groups

Four kinds of poly(ethylene glycol) (PEG) derivatives with the similar backbone and different side groups have been synthesized successfully. When both catecholamine and double bond are tethered to polymer backbone, i.e., the PEG backbone, simultaneously, the polymer can accelerate the curing speed of ethyl α‐cyanoacrylate (commercially available as 502) greatly under the same conditions (the curing time of such system is no more than 5 s). Probably this is due to the autoxidation of catecholamines. Through the redox‐cycling, catecholamines can produce, collect free radicals, and thus initiate the free radical polymerization. Due to the fast‐curing of such material when mixed with α‐cyanoacrylate, we could design and develop a new bicomponent super bioglue used in the dentistry or other bioenvironment requiring super fast settlement for further surgical operations.     

Small World Effects in a Harmonious Unifying Hybrid Preferential Model Networks

Small world effects in the harmonious unifying hybrid preferential model (HUHPM) networks are studied both numerically and analytically. The idea and method of the HUHPM is applied to three typical examples of unweighted BA model, weighted BBV model, and the TDE model, so-called HUHPM-BA, HUHPM-BBV and HUHPM-TDE networks. Comparing the HUHPM with current typical models above, it is found that the HUHPM networks has the smallest average path length and the biggest average clustering coefficient. The results demonstrate that the HUHPM is more suitable not only for the un-weighted models but also for the weighted models.     

高效率激光二极管泵浦100 Hz 3.5 J Nd∶YAG MOPA激光器

研制了结构简单、高效率激光二极管泵浦Nd∶YAGM0PA激光器.振荡级输出单脉冲能量1.13 J,重复频率为100HZ.MOPA系统输出最大单脉冲能量2.35 J,光-光转换效率为39%.实验结果和理论计算符合较好.     

分布式冷热电三联供系统的单耗分析模型研究

基于"单耗分析"理论,建立了针对燃料为天然气的分布式冷、热、电三联产系统的常见运行模式下的多热源、多冷源的燃料单耗模型和成本单耗模型.利用该模型进行了案例计算,结果清楚地表明了系统各个环节燃料附加单耗的分布.通过对计算结果的分析,得出了一些有益的结论.     

低压闪蒸液滴形态和温度变化的研究

将液滴在常压下突然置于低压环境中,液滴由最初的平衡状态变成过热状态,发生闪蒸.本文实验研究了低压闪蒸液滴内部形态和温度的变化,系统描述了液滴闪蒸过程中的各种形态变化,总结了稳态闪蒸和稳态结冰过程中环境压力和初始温度对温度变化的影响.实验结果表明液滴闪蒸分六种形态.稳态闪蒸中环境压力越低,液滴的最终温度也越低;液滴的初始温度越高,降到最低温度的时间越长.稳态结冰过程中,液滴初始温度增加,液滴结冰温度和结冰回升最高温度也随之增加;液滴的结冰温度和回升最高温度随环境压力的增高而减小.     

Sensitivity of Exponents of Three-Power Laws to Hybrid Ratio in Weighted HUHPM

The sensitivity of exponents of three-power laws for node degree, node strength and edged weight to hybrid ratio are studied analytically and numerically in the weighted harmonious unifying hybrid preferential model （HUHPM）, which is extended from an-weighted hybrid preferential attachment model we proposed previously [Chin. Phys. Lett. 22 （2005）719]. Our weighted HUHPMs plus the Barrat-Barthelemy-Vespignani model and the traffic-driven evolution model, respectively, are taken as two typical examples for demonstration and application of the HUHPM.     

Fluctuation of Quantum Information Density in Curved Time-Space

A dynamical equation for quantum information density （QID） in curved spacetime is presented. The related fluctuation of QID with quantum Einstein equation is also discussed, which reveals the measuring of the dynamical mutual information condition using a Gaussian quantum channel.