A simple,fast, and accurate thermodynamic‐based approach for transfer and prediction of gas chromatography retention times between columns and instruments Part I: Estimation of reference column geometry and thermodynamic parameters

The transfer of retention times based on thermodynamic models between columns can aid in separation optimization and compound identification in gas chromatography. Although earlier investigations have been reported, this problem remains unsuccessfully addressed. One barrier is poor predictive accuracy when moving from a reference column or system to a new target column or system. This is attributed to challenges associated with the accurate determination of the effective geometric parameters of the columns. To overcome this, we designed least squares‐based models that account for geometric parameters of the columns and thermodynamic parameters of compounds as they partition between mobile and stationary phases. Quasi‐Newton‐based algorithms were then used to perform the numerical optimization. In this first of three parts, the model used to determine the geometric parameters of the reference column and the thermodynamic parameters of compounds subjected to separation is introduced. As will be shown, the overall approach significantly improves the predictive accuracy and transferability of thermodynamic data (and retention times) between columns of the same stationary phase chemistry. The data required for the determination of the thermodynamic parameters and retention time prediction are obtained from fast and simple experiments. The proposed model and optimization algorithms were tested and validated using simulated and experimental data.     

A simple,fast, and accurate thermodynamic‐based approach for transfer and prediction of gas chromatography retention times between columns and instruments Part III: Retention time prediction on target column

This is the third part of a three‐part series of papers. In Part I, we presented a method for determining the actual effective geometry of a reference column as well as the thermodynamic‐based parameters of a set of probe compounds in an in‐house mixture. Part II introduced an approach for estimating the actual effective geometry of a target column by collecting retention data of the same mixture of probe compounds on the target column and using their thermodynamic parameters, acquired on the reference column, as a bridge between both systems. Part III, presented here, demonstrates the retention time transfer and prediction from the reference column to the target column using experimental data for a separate mixture of compounds. To predict the retention time of a new compound, we first estimate its thermodynamic‐based parameters on the reference column (using geometric parameters determined previously). The compound's retention time on a second column (of previously determined geometry) is then predicted. The models and the associated optimization algorithms were tested using simulated and experimental data. The accuracy of predicted retention times shows that the proposed approach is simple, fast, and accurate for retention time transfer and prediction between gas chromatography columns.     

Numerical Experiences with New Truncated Newton Methods in Large Scale Unconstrained Optimization

Recently, in [12] a very general class oftruncated Newton methods has been proposed for solving large scale unconstrained optimization problems. In this work we present the results of an extensive numericalexperience obtained by different algorithms which belong to the preceding class. This numerical study, besides investigating which arethe best algorithmic choices of the proposed approach, clarifies some significant points which underlies every truncated Newton based algorithm.     

Global and superlinear convergence of the smoothing Newton method and its application to general box constrained variational inequalities

The smoothing Newton method for solving a system of nonsmooth equations , which may arise from the nonlinear complementarity problem, the variational inequality problem or other problems, can be regarded as a variant of the smoothing method. At the th step, the nonsmooth function is approximated by a smooth function , and the derivative of at is used as the Newton iterative matrix. The merits of smoothing methods and smoothing Newton methods are global convergence and convenience in handling. In this paper, we show that the smoothing Newton method is also superlinearly convergent if is semismooth at the solution and satisfies a Jacobian consistency property. We show that most common smooth functions, such as the Gabriel-Moré function, have this property. As an application, we show that for box constrained variational inequalities if the involved function is -uniform, the iteration sequence generated by the smoothing Newton method will converge to the unique solution of the problem globally and superlinearly (quadratically).

     

Some notes on split Newton iterative algorithm

In this study, a parameterized split Newton method is derived by using the accelerating technique. Convergence and error estimates of the method are obtained. In practical application, the proposed method can give a better result in view of computational CPU time. Numerical examples on several partial differential equations are shown to illustrate our findings. Copyright © 2015 John Wiley & Sons, Ltd.     

牛顿环干涉法测量液体折射率的实验研究

利用牛顿环干涉法测量了水、乙醇和不同浓度的葡萄糖溶液的折射率,其实验结果与理论值符合的较好。实验过程中发现选用更大曲率半径的牛顿环能够有效降低干涉条纹的计数难度。     

Finding the transition state without initial guess: the growing string method for Newton trajectory to isomerization and enantiomerization reaction of alanine dipeptide and poly(15)alanine

We report a new, high-dimensional application of a method for finding a transition state (TS) between a reactant and a product on the potential energy surface: the search of a growing string along a reaction path defined by any Newton trajectory in combination with the Berny method (Quapp, J Chem Phys (2005), 122, 174106; we have provided this algorithm on a web page). Two given minima are connected by a one-dimensional, but usually curvilinear reaction coordinate. It leads to the TS region. The application of the method to alanine dipeptide finds the TS of the isomerisation C(7 ax) --> C(5), some TSs of the enantiomerisation of C(7 ax) from L-form to quasi-D-form, and it finds the TS region of a transition of a partly unfolded, bent structure which turns back into a mainly alpha-helix in the Ac(Ala)(15)NHMe polyalanine (all at the quantum mechanical level B3LYP/6-31G: the growing string calculation is interfaced with the Gaussian03 package). The formation or dissolvation of some alpha- or 3(10)-hydrogen bonds of the helix are discussed along the TS pathway, as well as the case of an enantiomer at the central residue of the helix.     

Calculating the branch points of the eigenvalues of the Coulomb spheroidal wave equation

A method for computing the eigenvalues λ _mn (b, c) and the eigenfunctions of the Coulomb spheroidal wave equation is proposed in the case of complex parameters b and c. The solution is represented as a combination of power series expansions that are then matched at a single point. An extensive numerical analysis shows that certain b _s and c _s are second-order branch points for λ _mn (b, c) with different indices n ₁ and n ₂, so that the eigenvalues at these points are double. Padé approximants, quadratic Hermite-Padé approximants, the finite element method, and the generalized Newton method are used to compute the branch points b _s and c _s and the double eigenvalues to high accuracy. A large number of these singular points are calculated.     

中心力场中散射角的简洁推导

本文从牛顿方程及角动量守恒定律出发 ,利用矢量函数的微积分运算技巧简捷地推导出中心力场中散射角 φ,避免了经典教科书中从轨道方程出发推导出 φ的繁琐性 ,不仅计算简洁 ,而且物理过程明确 .