Long-Time Bath Correlations in the Pollak–Grabert–Hänggi Theory

We analyze some cases for which the Pollak–Grabert–Hänggi theory on the activated rate processes for generalized Langevin dynamics exhibits unexplained disagreements with numerical results. First we analyze carefully the PGH theory and we show that a kind of Markovian hypothesis implicitly made in the reasoning is sometimes violated. Then we propose modifications of the original theory in order to take into account the possible effects caused by this violation, and we compare the corrected results with simulations.     

银－2－羧基－4－溴苯基重氮氨基偶氮苯－Triton X－100－SDS显色体系的研究及应用

新三氮烯类试剂之一，２－羧基－４－溴苯基重氮氨基偶氮苯，在ｐＨ１１．０的Ｎａ_２Ｂ_４Ｏ_７－ＮａＯＨ缓冲介质中，有非离子表面活性剂ＴｒｉｔｏｎＸ－１００及阴离子表面活性剂ＳＤＳ的共同存在下，可与Ａｇ（Ⅰ）生成稳定的２∶１红色配合物，红色配合物的λ_（ｍａｘ）＝５４０ｎｍ，表观摩尔吸光系数ε_（５４０）＝１．１０×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１）。Ａｇ量在０－１０μｇ／２５ｍＬ符合比尔定律。方法用于工业废水中痕量Ａｇ的测定，结果满意。     

2-氨基苯硫酚NIR-SERS光谱及其在纳米银表面吸附行为分析

本文采用静电自组装的方法制备了二维纳米银膜。UV-vis吸收光谱显示其等离子体共振吸收带位于400+900nm的光谱范围,延伸到了近红外区,可以较好的匹配785nm的近红外激发光源。以该纳米银膜为基底,对2-氨基苯硫酚(2-ATP)分子进行了近红外表面增强拉曼散射(NIR-SERS)检测,获得了重复性良好的NIR-SERS光谱图。实验表明:以2-ATP为探针分子时,该纳米银膜的NIR-SERS增强因子达到2.19×109。同时,本文采用密度泛函理论(DFT),以B3LYP/6-31G为基函数,对2-ATP分子进行结构优化和普通拉曼光谱(NR)计算,发现理论值和实验值吻合较好。此外,对2-ATP的NIR-SERS谱带进行了归属分析,发现当2-ATP分子在纳米银表面吸附时,是以-SH基团吸附到银表面,且同时-SH基团会被纳米银氧化。     

OH+C2H3F的反应机理及产物支化比反应的理论研究

本文对HOC₂H₃F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d,p)计算,同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH₂CHO+HF最有利的反应途径是OHC₂H₃F→i2→TS14→i6→TS9→i3→TS3→CH₂CHO+HF,其中速率决定步骤是HF通过TS11从CO桥接位置解离,能量比反应物高3.8 kcal/mol. 借助中间态TS14,F原子从C_α迁移到C_β位置生成CH₂O+CH₂F,然后通过中间态TS16,H从O迁移到C_α位置;通过中间态TS5,C-C键断裂生成产物,其能量比反应物低1.8 kcal/mol,比TS11低4.0 kcal/mol.     

F−(H2O)+CH3I配体交换反应动力学

本文介绍F^?(H₂O)+CH₃I→[FCH₃I]^?+H₂O在交叉分子束碰撞能量0.3∽2.6 eV的配体交换动力学成像结果. 产物的动能受到弱键结合配合物的稳定性的影响,大量水分子的内部激发不利于中间物有效的能量重新分配,随着碰撞增加,低动能受到抑制. 在0.3 eV时,内部亲核取代非常重要,为形成I^?和I^?(H₂O)的竞争性亲核取代途径提供了依据.     

Xe对NO(X)微分截面和非弹性散射中的碰撞诱导旋转准直

本文对NO(X)-Xe碰撞系统在碰撞能量为519 cm^-1,测量了完全?-双峰分解的微分截面和碰撞引起的旋转准直力矩. 同时结合初始量子态选择,使用六极杆的非均质电场,借助量子态分辨的测量,利用(1+1'')共振增强的多光子电离和速度离子成像. 结果显示,微分截面以及偏振相关的微分截面均显示与从头算势能面上进行的量子力学散射计算[J. K?os etal. J. Chem. Phys. 137, 014312 (2012)]一致. 通过与准经典轨迹、硬壳势能的量子力学散射以及运动近端模型的比较,评估了势能对所测微分截面和碰撞引起的旋转准直力矩的影响.     

一种生物柴油代用品在HZSM-5分子筛催化剂上的催化热解

为了深入了解生物柴油在ZSM-5沸石上的催化反应机理,在常压的流动反应器中进行了生物柴油代用品丁酸甲酯在氢型ZSM-5(HZSM-5)催化剂上的热解和催化热解. 热解产物使用气相色谱-质谱法定性和定量测量. 动力学模型和实验表明,气相中氢提取反应是热解过程中丁酸甲酯分解的主要途径,但在HZSM-5上,丁酸甲酯则主要通过解离生成烯酮和甲醇消耗;与无催化反应相比,丁酸甲酯在HZSM-5上的初始分解温度降低了约300 K. 并且通过Arrhenius方程获得了在催化热解和均相热解条件下丁酸甲酯消耗的表观活化能. 明显降低的表观活化能证实了HZSM-5对丁酸甲酯热解的催化性能. 此外催化剂的活化温度对HZSM-5的某些催化性能具有一定的影响. 该研究对进一步的实际生物柴油燃料的催化燃烧具有一定的指导意义.     

U-branes and T fibrations

We describe eight-dimensional vacuum configurations with varying moduli consistent with the U-duality group . Focusing on the latter less-well understood properties, we construct a class of fivebrane solutions living on lines on a three-dimensional base space. The resulting U-manifolds, with five scalars transforming under SL(3), admit a Ricci-flat Kähler metric. Based on the connection with special Lagrangian T³ fibered Calabi-Yau three-folds, this construction provides a simple framework for the investigation of Calabi-Yau mirrors.     

Synthesis of silver nanoparticles by sonogalvanic replacement on aluminium powder in sodium polyacrylate solutions

The process of the formation of silver nanoparticles (AgNPs) via the method of galvanic replacement (GR) of Ag⁺ with aluminum powder in sodium polyacrylate (NaPA) solutions in the ultrasonic (US) field has been studied. It was observed, that the yellow colloidal solutions of stabilized AgNPs with the absorption maximum at ∼ 410 nm were obtained under the application of US power by 20 W and frequency by 20 kHz in the wide range of AgNO₃ and NaPA concentrations (0.1 – 0.5 mM and 0.5 – 5.0 g/L respectively) at 25 ⁰C. It was shown, that the GR process under US field occurs without of the significant induction period. Using the UV–vis spectroscopy the kinetics of AgNPs formation has been studied and it was observed the first order kinetics with respect to Ag⁺ ions both for the nucleation and growth processes. It was found that observable rate constants of nucleation are close for the all experimental conditions but the observable rate constants of growth decreased with increasing of initial concentration of AgNO₃. Based on the obtained kinetic data it was proposed a mechanism of the formation of AgNPs consisted of the following two main stages: 1) the nucleation with the formation of primary nanoclusters (AgNCs) on aluminum surface followed by their ablation from the surface of the sacrificial metal by ultrasound into bulk of solution; 2) the transformation of AgNCs in AgNPs via growth from the Al surface and / or agglomeration of AgNCs. Using TEM it was found that the size of obtained AgNPs does not exceed of 25 nm and slightly depends on the initial concentrations of precursors. High antimicrobial activity of obtained colloidal solutions against gram-negative and gram-positive bacteria as well as against fungi was observed.     

Experimental study on laser cleaning of paint layer on white marble surface北大核心CSCD

In order to effectively remove the surface paint of the cultural relic of white marble, the area extrapolation method and laser-induced plasma spectroscopy (LIPS) method were used to obtain the ablation threshold power of the gold, silver paint layer and white marble surface. On the basis of this, the optimal laser power for removing paint without damaging the white marble substrate was determined. The image processing method was used to study the cleaning degree and variation trend of cleaning rate of the gold and silver paint on the surface of 10 mm×10 mm white marble by laser cleaning, and the optimal laser spot overlap rate and the optimal cleaning times were obtained. Finally, the image processing method was used to evaluate the cleaning effect of laser cleaning of paint layer on the white marble surface. More than 93% of the cleaning degree shows that the synergistic use of the area extrapolation method, LIPS method and image processing method can effectively improve the laser cleaning efficiency of the paint layer on white marble surface. Copyright ©2022 Journal of Applied Optics. All rights reserved.