Band splitting in overloaded isocratic elution chromatography I. The experimental evidence

A series of samples of increasing volume (from 0.001 to 4.0 cm3), containing the same constant concentration (40 g/l) of two simple compounds, ethylbenzoate and 4-tert.-butylphenol were injected on a Kromasil-C18 column with methanol-water (62:38. v/v) as the mobile phase. Complex band profiles were observed when the volume of the sample became large enough and strong band interference took place. The analysis of the fractions collected during the elution of the mixed band demonstrates that, for samples larger than 2 cm3, the band of 4-tert.-butylphenol is split into two separate bands, one eluted before and the other eluted after the band of ethylbenzoate. Such a phenomenon has never been observed yet in RPLC, under isocratic elution conditions.     

Potential energy surfaces and nonadiabatic transitions in the asymptotic regions of ICN photodissociation to study the interference effects in the F1 and F2 spin-rotation levels of the CN products

One of the most spectacular yet unsolved problems for the ICN -band photodissociation is the non-statistical spin-rotation F₁ = N + 1/2 and F₂ = N − 1/2 populations for each rotation level N of the CN fragment. The F₁/F₂ population difference function f(N) exhibits strong N and λ dependences with an oscillatory behavior. Such details were found to critically depend on the number of open-channel product states, namely, whether both I (²P_3/2) and I (²P_1/2) are energetically available or not as the dissociation partner. First, in the asymptotic region, the exchange and dipole-quadrupole inter-fragment interactions were studied in detail. Then, as the diabatic basis, we took the appropriate symmetry adapted products of the electronic and rotational wavefunctions for the F₁ and F₂ levels at the dissociation limits. We found that the adiabatic Hamiltonian exhibits Rosen–Zener–Demkov type nonadiabatic transitions reflecting the switch between the exchange interaction and the small but finite spin-rotation interaction within CN at the asymptotic region. This non-crossing type nonadiabatic transition occurs with the probability 1/2, that is, at the diabatic limit through a sudden switch of the quantization axis for CN spin S from the dissociation axis to the CN rotation axis N . We have derived semiclassical formulae for f(N) and the orientation parameters with a two-state model including the 3A′ and 4A′ electronic states, and with a four-state model including the 3A′ through 6A′ electronic states. These two kinds of interfering models explain general features of the F₁ and F₂ level populations observed by Zare's group and Hall's group, respectively. © 2018 Wiley Periodicals, Inc.     

The catanionic system dodecyltrimethylammonium hydroxide–n-dodecanephosphonic acid–water. Triangular phase diagram

 The triangular phase diagram of the system dodecyltri-methylammonium hydroxide (DTAOH)–dodecanephosphonic acid (H₂DP)–water was studied by several techniques. The DTAOH-rich zone could not be studied because DTAOH decomposed when it was dried. Pure H₂DP only forms lamellar mesophases with water. The inclusion of DTAOH in the system produces the appearance of cubic and hexagonal mesophases. The gradual increase in DTAOH proportion lead to the gradual reduction in the existence of the lamellar mesophase domain, and increase of the hexagonal liquid crystal domain. At high DTAOH content, the lamellar mesophase disappeared. This behavior was explained by the gradual destruction of the hydrogen-bonded structure in the polar headgroup layer of liquid crystal aggregates. H₂DP-rich anhydrous crystals were triclinic. Received: 8 September 1997 Accepted: 17 February 1998     

RESERVOIR DESCRIPTION BY USING A PIECEWISE CONSTANT LEVEL SET METHOD

We consider the permeability estimation problem in two-phase porous media flow. We try to identify the permeability field by utilizing both the production data from wells as well as inverted seismic data. The permeability field is assumed to be piecewise constant, or can be approximated well by a piecewise constant function. A variant of the level set method, called Piecewise Constant Level Set Method is used to represent the interfaces between the regions with different permeability levels. The inverse problem is solved by minimizing a functional, and TV norm regularization is used to deal with the ill-posedness. We also use the operator-splitting technique to decompose the constraint term from the fidelity term. This gives us more flexibility to deal with the constraint and helps to stabilize the algorithm.     

类氢氖在高温高密度等离子体中的光谱漂移

 采用离子球模型,通过自洽求解Poisson方程和Dirac方程,得到氖的类氢离子低能级组态的能级能量随等离子体电子温度和电子密度的变化关系,进一步研究了等离子体电子温度和电子密度对光谱漂移的影响。结果表明：光谱漂移随着等离子体电子密度的增大而增大,随着电子温度的升高而减小;谱线精细结构分裂随着电子密度的增大而减小,随着电子温度的升高而增大。等离子体对束缚电子的屏蔽是决定光谱漂移的主要原因。这些变化规律不仅对等离子体光谱模拟结果产生影响,而且使实验上观测光谱的相对或绝对漂移成为可能,从而为高密度等离子体诊断的新方法提供了理论依据。     

碳自掺杂石墨相氮化碳纳米片的制备及其在可见光照射下的光解水产氢性能

石墨相氮化碳(g-C3N4)由于具有对可见光吸收范围较窄和光生载流子分离效率低等缺陷,其光解水产氢活性较差.我们采用简单的一步热共聚法,以尿素和2,4,6-三氨基嘧啶(TAPD)混合物为前驱物,制备碳自掺杂纳米片(CNNS-x,xmg代表掺入TAPD的质量).X射线衍射(XRD)、元素分析(EA)和X射线光电子能谱(X...     

单原子催化剂在电化学中的研究进展

目前单原子催化剂的研究呈现爆发式增长, 已然成为材料科学和催化领域的明星材料和研究热点. 前期报道的单原子催化剂研究主要针对某一个应用方向进行探讨, 较少研究催化剂的双功能或多功能应用. 近年来, 为了拓展单原子催化剂在更多领域和方向的应用, 具有双功能甚至多功能的单原子催化剂的设计开发备受关注. 本文综合评述了近年来具有双功能活性的单原子催化剂的研究进展, 重点介绍了其在电化学领域中的最新应用研究. 最后, 对具有双功能活性的单原子催化剂发展研究中存在的问题进行了简要分析, 并对未来发展前景进行了展望.     

光电解水制氢耦合生物质醇/醛氧化的研究进展

生物质醇/醛是一类重要的生物基平台化合物, 通过催化氧化重整可将其进一步转化为高值含氧化学品或燃料. 太阳能驱动的光电催化技术是实现生物质醇/醛氧化最为绿色高效的途径之一. 与传统光电解水制氢相比, 利用生物质醇/醛氧化来替代阳极析氧过程不仅可以提高阳极产物的附加值, 同时可以提升太阳能到氢能的转化效率. 因此, 光电解水制氢耦合生物质醇/醛氧化对绿氢提效降本和高值化学品合成具有重要意义. 本文综合评述了光电解水制氢耦合生物质醇/醛的氧化反应机理, 总结了目前光电催化技术在生物质醇/醛氧化方面的研究进展, 最后对该领域所面临的机遇和挑战进行了展望.     

磁场效应对理解水分解反应物的可能意义

电催化水分解由两个基元反应构成,即析氢反应(HER)和析氧反应(OER).开发强大的HER和OER技术需要在分子层面理解反应机理,然而,目前水分解反应的反应物还没有完全确定.本文利用磁场来研究HER中的质子传输和OER中的氢离子传输,对确定HER和OER中真实的反应物具有重要意义.磁场是改变离子等带电物质运动的一种有效...     

AUFS格式在无网格方法中的应用

将计算量小,激波分辨率高的AUFS (artificially upstream flux vector splitting) 格式应用于无网格方法. 所发展算法基于多项式基函数最小二乘无网格方法,采用线性基函数曲面拟合及AUFS 格式计算各离散点的空间导数,应用四阶Runge-Kutta 法进行时间显式推进. 为验证算法健壮性、精度以及计算效率,对Riemann 问题、超音速平面流动,以及不同攻角NACA0012 翼型跨音速流场进行了数值模拟,其结果同采用HLLC (Harten-Lax-van Leer-contact) 格式的无网格方法以及文献报道结果吻合较好,并且计算量较形式简单HLLC 格式减少约15%.