非恒稳含时电极过程中涨落-耗散的电化学效应——恒电势滴汞电极体系的随机热力学模型

以滴汞电极体系为模型,对非恒稳恒电势动态不可逆电极过程中的耗散-涨落效应进行了系统的研究.基于滴汞电极体系的电化学特征,提出了一个简化的含时随机热力学模型,从而可能对这类重要的含时物理化学过程进行涨落和耗散的定量分析.借助该简化的模型,成功地建立了恒电势滴汞电极过程的基本随机热力学公式,由此推出耗散-涨落效应的理论极谱曲线.在滴汞电极生长缓慢及扩散步骤严重滞后情况下,含时的滴汞电极过程将趋于在有效扩散层厚度演化的慢流型上的准定态过程.在这种准定态近似下,具体分析了涨落对极谱曲线的影响.结果表明,在涨落影响可以忽略的近平衡区,从耗散-涨落导出的极谱方程与从平衡态Nernst公式导出的极谱方程完全吻合.还计算了一个涨落诱导的极谱曲线偏离的典型范例.     

聚合物体系散射函数的热力学基础

利用链段浓度和链头浓度的概念，根据热力学涨落理论，给出了聚合物二元共混体系ｄｅＧｅｎｎｅｓ散射函数的一个普遍的热力学证明，指出了这个函数和Ｆｌｏｒｙ－Ｈｕｇｇｉｎｓ共混自由能公式一样，也依赖于忽略构象涨落的假设．     

化合物结构／性质相关的研究／拓扑指数法（Ⅰ）

本文提出一种新的拓扑指数－ＥＡ系列指数，它是从表示分子图形的邻接矩阵出发，结合图形中顶点的度构造成ＥＡ矩阵，计算ＥＡ矩阵的本征值，求出本征值绝对值和指数ＥＡΣ及本征值绝对值最大值指数ＥＡｍａｘ，实验表明，ＥＡ系列指数具有良好的唯一性和相关性。     

有关简并与对称性的几个问题

有关简并与对称性的几个问题何伯珩（华中师范大学化学系，武昌４３００７０）量子力学体系常常出现简并。即对应于某一能量，存在不止一个能量本征态。常称属于Ｅ的独立的本征态数ｓ为简并度。一般他说，简并是体系对称性的表现。但简并是否均由对称性产生？体系的对称性...     

一个纳入活化络合非平衡效应的TST公式体系

在唯象理论的层次上评述了活化络合体系的非平衡性引起的非平衡统计问题;通过分析活化络合过程的耗散与涨落对反应速度的影响,提出了一个纳入了活化络合过程非平衡效应的TST公式体系代替活化络合平衡常数,建立了活化络合耗散函数与反应速度的关系.同时讨论了影响反应活化络合进程耗散-涨落的诸因素所导致的速度常数统计漂移     

希土水杨酸与8─羟基喹啉三元配合物研究

合成了六种希土（ＲＥ）－水杨酸（Ｈ２ｓａｌ）－８－羟基喹啉（Ｈｈｑ）三元固体配合物，其通式为ＲＥ（Ｈｓａｌ）２·ｈｑ（ＲＥ＝Ｙ，Ｌａ，Ｎｄ，Ｓｍ，Ｈｏ，Ｅｒ）．通过元素分析、摩尔电导、ＩＲ、Ｆａｒ－ＩＲ、ＵＶ－Ｖｉｓ、ＴＧ－ＤＴＡ分析，研究了配合物的组成、性质和成键特性．通过抑菌试验表明配合物对于霉菌具有抑真菌能力．     

选择性接聚乙二醇枝聚醚聚酯的合成及其血液相容性

水解α－甲基－ω（２，３－环氧）丙基聚乙二醇（Ⅱ）得到接有聚乙二醇（ＰＥＧ）枝的丙二醇（Ⅲ），用其与对苯二甲酰氯及聚丁二醇反应制得在硬链段接有ＰＥＧ枝的聚醚聚酯（Ｈ－ＰＥＥｓ），以四氢呋喃与Ⅱ进行正离子开环共聚合制得每他链接有１．２５个ＰＥＧ枝的聚丁二醇（ＩＶ），用Ⅳ合成了在软链上接ＰＥＧ枝的聚醚聚酯（Ｓ－ＰＥＥｓ），不同位置接权的ＰＥＥｓ亲水性均较母体明显改进，抗凝血性则以Ｈ－ＰＥＥｓ改进显著。     

GaAs／AlxGa1—xAs量子阱电极／非水溶液界面性能的研究

用阻抗谱研究了晶格匹配型单、多量子阱ＧａＡｓ／ＡｌｘＧａ１－ｘＡｓ电极在二茂铁乙腈溶液中的界面性能。得到了空间电荷层电容及表面态电容与电极电位的依赖关系。空间电荷电容与量子阱电极的结构有关，而表面态电容则决定于电极的表面性质如表面氧化层及二茂铁的吸附。分析和讨论了表面态的能级，密度的分布，来源和作用。     

示波催化极谱法测定钢中微量钼

采用ＥＧＴＡ－丙二酸复合掩蔽体系，苯羟乙酸－氯酸盐催化体系，示波极谱法直接测定了多种合金钢中的微量钼，方法操作简单，结果可靠，灵敏度高。     

梳状高分子固体电解质的离子导电性研究

深入研究了交替马来酸酐共聚物多缩乙二醇酯（ＣＰ３５０）两种锂盐络合物ＣＰ３５０／ＬｉＡｓＦ＿６和ＣＰ３５０／ＬｉＰＦ＿６的离子传导性能,给出了与复阻抗谱相对应的等效电路．离子电导率随［Ｌｉ］／［ＥＯ］的变化而出现一极大值,室温下,两体系电导率极大值分别为１．３８×１０（－４）,８．３２×１０（－５）Ｓ／ｃｍ．电导率随温度升高而增加．导电行为呈非－Ａｒｒｈｅｎｉｕｓ特征．阴阳离子半径之和（ｒ＿ｃ＋ｒ＿ａ）愈大,离子电导率愈高．     

Semiclassical initial value series representation in the continuum limit: application to vibrational relaxation

A recently formulated continuum limit semiclassical initial value series representation (SCIVR) of the quantum dynamics of dissipative systems is applied to the study of vibrational relaxation of model harmonic and anharmonic oscillator systems. As is well known, the classical dynamics of dissipative systems may be described in terms of a generalized Langevin equation. The continuum limit SCIVR uses the Langevin trajectories as input, albeit with a quantum noise rather than a classical noise. Combining this development with the forward-backward form of the prefactor-free propagator leads to a tractable scheme for computing quantum thermal correlation functions. Here we present the first implementation of this continuum limit SCIVR series method to study two model problems of vibrational relaxation. Simulations of the dissipative harmonic oscillator system over a wide range of parameters demonstrate that at most only the first two terms in the SCIVR series are needed for convergence of the correlation function. The methodology is then applied to the vibrational relaxation of a dissipative Morse oscillator. Here, too, the SCIVR series converges rapidly as the first two terms are sufficient to provide the quantum mechanical relaxation with an estimated accuracy on the order of a few percent. The results in this case are compared with computations obtained using the classical Wigner approximation for the relaxation dynamics.     

Influence of environment induced correlated fluctuations in electronic coupling on coherent excitation energy transfer dynamics in model photosynthetic systems

Two-dimensional photon-echo experiments indicate that excitation energy transfer between chromophores near the reaction center of the photosynthetic purple bacterium Rhodobacter sphaeroides occurs coherently with decoherence times of hundreds of femtoseconds, comparable to the energy transfer time scale in these systems. The original explanation of this observation suggested that correlated fluctuations in chromophore excitation energies, driven by large scale protein motions could result in long lived coherent energy transfer dynamics. However, no significant site energy correlation has been found in recent molecular dynamics simulations of several model light harvesting systems. Instead, there is evidence of correlated fluctuations in site energy-electronic coupling and electronic coupling-electronic coupling. The roles of these different types of correlations in excitation energy transfer dynamics are not yet thoroughly understood, though the effects of site energy correlations have been well studied. In this paper, we introduce several general models that can realistically describe the effects of various types of correlated fluctuations in chromophore properties and systematically study the behavior of these models using general methods for treating dissipative quantum dynamics in complex multi-chromophore systems. The effects of correlation between site energy and inter-site electronic couplings are explored in a two state model of excitation energy transfer between the accessory bacteriochlorophyll and bacteriopheophytin in a reaction center system and we find that these types of correlated fluctuations can enhance or suppress coherence and transfer rate simultaneously. In contrast, models for correlated fluctuations in chromophore excitation energies show enhanced coherent dynamics but necessarily show decrease in excitation energy transfer rate accompanying such coherence enhancement. Finally, for a three state model of the Fenna-Matthews-Olsen light harvesting complex, we explore the influence of including correlations in inter-chromophore couplings between different chromophore dimers that share a common chromophore. We find that the relative sign of the different correlations can have profound influence on decoherence time and energy transfer rate and can provide sensitive control of relaxation in these complex quantum dynamical open systems.     

Effect of noise on the classical and quantum mechanical nonlinear response of resonantly coupled anharmonic oscillators

Multidimensional infrared spectroscopy probes coupled molecular vibrations in complex, condensed phase systems. Recent theoretical studies have focused on the analytic structure of the nonlinear response functions required to calculate experimental observables in a perturbative treatment of the radiation-matter interaction. Classical mechanical nonlinear response functions have been shown to exhibit unbounded growth for anharmonic, integrable systems, as a consequence of the nonlinearity of classical mechanics, a feature that is absent in a quantum mechanical treatment. We explore the analytic structure of the third-order vibrational response function for an exactly solvable quantum mechanical model that includes some of the important and theoretically challenging aspects of realistic models of condensed phase systems: anharmonicity, resonant coupling, fluctuations, and a well-defined classical mechanical limit.     

Characterization of quantum dynamically significant paths of bridge-mediated charge transfer systems

In this article, we examine characteristics of quantum dynamically important paths using the on-the-fly filtered propagator functional path integral method, which evaluates a numerically accurate reduced density matrix by ignoring the vast majority of paths with insignificant contribution to the dynamics of interest. Two five-state charge-transfer systems have been considered, such that each system is governed by a different charge-transfer mechanism. It was found that, for the incoherent hopping transfer, the quantum mechanically important paths mimic classical counterparts that show little deviation between forward and backward path. Therefore, it is desirable to take advantage of a priori knowledge of the important path characteristics; in particular, it is possible to evaluate the accurate dynamics of bridge-mediated long-range charge-transfer systems efficiently in a significantly reduced quantum mechanical trajectory space.     

Relaxation of quantum hydrodynamic modes

In this article, we develop a series of hierarchical mode‐coupling equations for the momentum cumulants and moments of the density matrix for a mixed quantum system. Working in the Lagrange representation, we show how these can be used to compute quantum trajectories for dissipative and nondissipative systems. This approach is complementary to the de Broglie–Bohm approach in that the moments evolve along hydrodynamic/Lagrangian paths. In the limit of no dissipation, the paths are the Bohmian paths. However, the “quantum force” in our case is represented in terms of momentum fluctuations and an osmotic pressure. Representative calculations for the relaxation of a harmonic system are presented to illustrate the rapid convergence of the cumulant expansion in the presence of a dissipative environment. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

两种体系中多重随机共振的噪声调控

通过计算机模拟,介绍一种新的方法来控制两种体系中的多重随机共振,被控参数选为噪声的脉冲间隔或噪声强度.对于对称的二能级的量子耗散体系,调节量子噪声则可以实现对量子多重随机共振的控制.另外还借用不同能级之间跃迁的观点来解释多重随机共振现象的形成机理.     

Relaxation and dephasing in open quantum systems time-dependent density functional theory: Properties of exact functionals from an exactly-solvable model system

The dissipative dynamics of many-electron systems interacting with a thermal environment has remained a long-standing challenge within time-dependent density functional theory (TDDFT). Recently, the formal foundations of open quantum systems time-dependent density functional theory (OQS-TDDFT) within the master equation approach were established. It was proven that the exact time-dependent density of a many-electron open quantum system evolving under a master equation can be reproduced with a closed (unitarily evolving) and non-interacting Kohn-Sham system. This potentially offers a great advantage over previous approaches to OQS-TDDFT, since with suitable functionals one could obtain the dissipative open-systems dynamics by simply propagating a set of Kohn-Sham orbitals as in usual TDDFT. However, the properties and exact conditions of such open-systems functionals are largely unknown. In the present article, we examine a simple and exactly-solvable model open quantum system: one electron in a harmonic well evolving under the Lindblad master equation. We examine two different representitive limits of the Lindblad equation (relaxation and pure dephasing) and are able to deduce a number of properties of the exact OQS-TDDFT functional. Challenges associated with developing approximate functionals for many-electron open quantum systems are also discussed.