MM3 parametrization of four‐ and five‐coordinated rhenium complexes by a genetic algorithm—Which factors influence the optimization performance?

Genetic algorithms (GA) were used to solve one of the multidimensional problems in computational chemistry, the optimization of force field parameters. The correlation between the composition of the GA, its parameters (p(c), p(m)) and the quality of the results were investigated. The composition was studied for all combinations of a Simple GA/Steady State GA with a Roulette Wheel/Tournament Selector using different values each for crossover (0.5, 0.7, 0.9) and mutation rates (0.01, 0.02, 0.05, 0.10, 0.20). The results show that the performance is strongly dependent on the GA scheme, where the Simple GA/Tournament Selector yields the best results. Two new MM3 parameters were introduced for rhenium compounds with coordination number four (204) and coordination number five (205), the formal oxidation states of rhenium ranging from +V to +VII. A manifold of parameters (Re-C, N, O, S) was obtained by using a diverse set of CSD structures. The advantage of the GA vs. UFF calculations is shown by comparison of several examples. The GA optimized parameters were able to reproduce the geometrical data of the X-ray structures.     

A revised quantum chemistry-based potential for poly(ethylene oxide) and its oligomers in aqueous solution

We have conducted a high-level quantum chemistry study of the interactions of 1,2-dimethoxyethane (DME) with water for complexes representing both hydrophilic and hydrophobic hydration. It was found that our previous quantum chemistry-based force field for poly(ethylene oxide) (PEO) and its oligomers in aqueous solution did a poor job in describing the hydrophobic binding of water to the ether, consistent with our recent calculations of the excess free energy and entropy of hydration of DME. Our original force field was revised to more accurately reproduce the interaction of water with the carboneous portions of DME. Molecular dynamics simulations of aqueous DME solutions using the revised quantum chemistry-based potential yielded good agreement with experiment for excess free energy, enthalpy, and volume as well as excess solution viscosity and the self-diffusion of water. Comparison with our original potential revealed that the relatively hydrophobic ether-water interactions in the new potential strongly reduced the favorable excess free energy and enthalpy but have relatively little influence on the excess entropy for dilute DME solutions. Other properties of DME and PEO solutions including conformational populations and dynamics, solution viscosity, hydrogen bonding, water translational and rotational diffusion and neutron structure factor as a function of solution composition were found to be largely unchanged from those obtained using the original potential.     

An improved CNDO/2 standard parametrization for bromine containing molecules

Bromine parameters are proposed, matching well the standard values of first and second row atoms, as introduced by Pople et al. This is shown by comparisons of geometries, configurations, conformations, and dipole moments, obtained with different approaches. The new parameter set was found in a very simple and efficient way that may also be useful for other tasks, e.g. in non-empirical calculations.     

紧支撑三元正交小波滤波器的参数化

高维小波分析是分析和处理多维数字信号的有力工具．非张量积多元小波被广泛地应用在模式识别、纹理分析和边缘检测等领域．本文给出方体域上三元正交滤波器的一种参数化构造算法,三元小波滤波器的这种构造方法使我们能更方便地研究非张量积的三元正交小波．最后给出数值算例．     

Comparison of structural,thermodynamic, kinetic and mass transport properties of Mg2+ ion models commonly used in biomolecular simulations

The prevalence of Mg²⁺ ions in biology and their essential role in nucleic acid structure and function has motivated the development of various Mg²⁺ ion models for use in molecular simulations. Currently, the most widely used models in biomolecular simulations represent a nonbonded metal ion as an ion‐centered point charge surrounded by a nonelectrostatic pairwise potential that takes into account dispersion interactions and exchange effects that give rise to the ion's excluded volume. One strategy toward developing improved models for biomolecular simulations is to first identify a Mg²⁺ model that is consistent with the simulation force fields that closely reproduces a range of properties in aqueous solution, and then, in a second step, balance the ion–water and ion–solute interactions by tuning parameters in a pairwise fashion where necessary. The present work addresses the first step in which we compare 17 different nonbonded single‐site Mg²⁺ ion models with respect to their ability to simultaneously reproduce structural, thermodynamic, kinetic and mass transport properties in aqueous solution. None of the models based on a 12‐6 nonelectrostatic nonbonded potential was able to reproduce the experimental radial distribution function, solvation free energy, exchange barrier and diffusion constant. The models based on a 12‐6‐4 potential offered improvement, and one model in particular, in conjunction with the SPC/E water model, performed exceptionally well for all properties. The results reported here establish useful benchmark calculations for Mg²⁺ ion models that provide insight into the origin of the behavior in aqueous solution, and may aid in the development of next‐generation models that target specific binding sites in biomolecules. © 2015 Wiley Periodicals, Inc.     

控制点优化磨光算法在长江径流量预测中的应用

盈亏修正磨光法所得到的逼近效果仍然很差,通过控制点的参数优化和目标函数的最小,提出一种控制点优化磨光算法,利用这个算法得到参数后代入模型,使预测的精度得到提高.通过实例,该算法简单易行,并通过相对误差进行了分析,控制点优化磨光算法所得到的预测值好于神经网络模型、PPAR和小波网络模型的预测值,这为研究磨光法提供了较好的分析方法.     

Clifford Algebras and Euclid’s Parametrization of Pythagorean Triples

We show that the space of Euclid’s parameters for Pythagorean triples is endowed with a natural symplectic structure and that it emerges as a spinor space of the Clifford algebra R₂₁, whose minimal version may be conceptualized as a 4-dimensional real algebra of “kwaternions.” We observe that this makes Euclid’s parametrization the earliest appearance of the concept of spinors. We present an analogue of the “magic correspondence” for the spinor representation of Minkowski space and show how the Hall matrices fit into the scheme. The latter obtain an interesting and perhaps unexpected geometric meaning as certain symmetries of an Apollonian gasket. An extension to more variables is proposed and explicit formulae for generating all Pythagorean quadruples, hexads, and decuples are provided.     

Some Indeterminate Moment Problems and Freud-Like Weights

We study two indeterminate Hamburger moment problems and the corresponding orthogonal polynomials. The coefficients in their recurrence relations are of exponential growth or are polynomials of degree 2. The entire functions in the Nevanlinna parametrization are found. The orthogonal polynomials with polynomial recurrence coefficients resemble the Freud polynomials with a = 1/2 . Inequalities are given for the largest zero and the asymptotic behavior of the largest zero is established. April 24, 1996. Date revised: March 3, 1997.     

Optimal control for nonlinear systems calculated with small computers

Using Ritz's procedure of representing the control functions of an optimal control problem by a function series with parameters to be optimized, it is shown that, from the well-known gradient procedure for dynamic problems, a simple iteration formula for the optimization of these parameters can be derived. Using an example with a technical background, the effectiveness of the program realization of this approach is demonstrated and is compared with the results of unrestricted dynamic optimization.This work was performed at the Technische Hochschule in Darmstadt, West Germany, with financial support from the DFG (Deutsche Forschungs-Gemeinschaft).