The W algorithm and the D transformation for the numerical evaluation of three‐center nuclear attraction integrals

Three‐center nuclear attraction integrals over exponential‐type functions are required for ab initio molecular structure calculations and density functional theory (DFT). These integrals occur in many millions of terms, even for small molecules, and they require rapid and accurate numerical evaluation. The use of a basis set of B functions to represent atomic orbitals, combined with the Fourier transform method, led to the development of analytic expressions for these molecular integrals. Unfortunately, the numerical evaluation of the analytic expressions obtained turned out to be extremely difficult due to the presence of two‐dimensional integral representations, involving spherical Bessel integral functions. % The present work concerns the development of an extremely accurate and rapid algorithm for the numerical evaluation of these spherical Bessel integrals. This algorithm, which is based on the nonlinear D transformation and the W algorithm of Sidi, can be computed recursively, allowing the control of the degree of accuracy. Numerical analysis tests were performed to further improve the efficiency of our algorithm. The numerical results section demonstrates the efficiency of this new algorithm for the numerical evaluation of three‐center nuclear attraction integrals. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Validating additive correction schemes against gradient-based extrapolations

The use of additive correction schemes to obtain structures and vibrational frequencies of increasingly larger molecules is becoming more common. Such approaches, based on the cubic extrapolation formula applied directly to the quantity of interest, have been successfully validated only at the highest levels of computational accuracy: for coupled cluster methods with comparably large basis sets. Here, a systematic validation of geometries and vibrational frequencies is carried out, including more affordable and relevant levels of theory, such as the Møller-Plesset perturbation theory applied with smaller basis sets. Comparisons of such additive schemes against the more rigorous gradient-based extrapolation are presented. The cbs () routine of the open-source quantum-chemistry package Psi4 has been extended for this purpose. The results confirm that geometries and frequencies of covalently bound species obtained with additive correction schemes are in an excellent agreement with the results of gradient-based extrapolations. However, when applied to systems involving noncovalent interactions, the errors due to such schemes are significantly larger. In general, we propose the application of gradient-based extrapolations, as they incur no extra cost compared to additive schemes.     

The local ultraconvergence of high‐order finite element method for second‐order elliptic problems with constant coefficients over a rectangular partition

In this article, we will discuss the local ultraconvergence of high‐degree finite element method based on a rectangular partition for the second‐degree elliptic problem with constant coefficients in Ω ? ?² , u( y ) = 0 on ?Ω . Based on suitable regularity, ultraconvergence of the displacement of the extrapolated kth (k ≥ 3) degree finite element solution has been obtained by an extrapolation technique. Finally, numerical experiments are applied to demonstrate our theoretical findings.     

Finding optimal finite field strengths allowing for a maximum of precision in the calculation of polarizabilities and hyperpolarizabilities

The finite field method, widely used for the calculation of static dipole polarizabilities or the first and second hyperpolarizabilities of molecules and polymers, is thoroughly explored. The application of different field strengths and the impact on the precision of the calculations were investigated. Borders could be defined and characterized, establishing a range of feasible field strengths that guarantee reliable numerical results. The quality of different types of meshes to screen the feasible region is assessed. Extrapolation schemes are presented that reduce the truncation error and allow to increase the precision of finite field calculations by one to three orders of magnitude. © 2013 Wiley Periodicals, Inc.     

广义sine-Gordon方程高精度隐式紧致差分方法

本文研究一类二维非线性的广义sine-Gordon(简称SG)方程的有限差分格式.首先构造三层时间的紧致交替方向隐式差分格式,并用能量分析法证明格式具有二阶时间精度和四阶空间精度.然后应用改进的Richardson外推算法将时间精度提高到四阶.最后,数值算例证实改进后的算法在空间和时间上均达到四阶精度.     

Focal Point Evaluation of Energies for Tautomers and Isomers for 3-hydroxy-2-butenamide: Evaluation of Competing Internal Hydrogen Bonds of Types -OH…O=, -OH…N, -NH…O=, and CH…X (X=O and N)

The title compound is a small molecule with many structural variations; it can illustrate a variety of internal hydrogen bonds, among other noncovalent interactions. Here we examine structures displaying hydrogen bonding between carbonyl oxygen and hydroxyl H; between carbonyl oxygen and amino H; hydroxyl H and amino N; hydroxyl O and amino H. We also consider H-bonding in its tautomer 2-oxopropanamide. By extrapolation algorithms applied to Hartree-Fock and correlation energies as estimated in HF, MP2, and CCSD calculations using the cc-pVNZ correlation-consistent basis sets (N = 2, 3, and 4) we obtain reliable relative energies of the isomeric forms. Assuming that such energy differences may be attributed to the presence of the various types of hydrogen bonding, we attempt to infer relative strengths of types of H-bonding. The Atoms in Molecules theory of Bader and the Local Vibrational Modes analysis of Cremer and Kraka are applied to this task. Hydrogen bonds are ranked by relative strength as measured by local stretching force constants, with the stronger =O…HO- > NH…O= > -OH…N well separated from a cluster > NH…O= ≈ >NH…OH ≈ CH…O= of comparable and intermediate strength. Weaker but still significant interactions are of type CH…N which is stronger than CH…OH.     

解弹性力学第二类边界积分方程的求积法与分裂外推

利用Sidi奇异求积公式,提出了解曲边多角形域上线性弹性力学第二类边界积分方程的求积法,即离散矩阵的每个元素的生成只需赋值不需计算任何奇异积分.通过估计离散矩阵的特征值和利用Anselone聚紧收敛理论,证明了近似解的收敛性;同时得到了误差的多参数渐近展开式;通过并行地解粗网格上的离散方程,利用分裂外推获得了高精度近似解和后验误差.     

求解Schrdinger方程的高阶紧致差分格式

基于Richardson外推法提出了一种求解Schrdinger方程的高阶紧致差分方法.该方法首先利用二阶微商的四阶精度紧致差分逼近公式对原方程进行求解,然后利用Richardson外推技术外推一次,得到了Schrdinger方程具有O(r~4+h~4)精度的数值解.通过Fourier分析方法证明了该格式是无条件稳定的.数值实验验证了该方法的高阶精度及有效性.     

On the Vector ε-Algorithm for Solving Linear Systems of Equations

The four vector extrapolation methods, minimal polynomial extrapolation, reduced rank extrapolation, modified minimal polynomial extrapolation and the topological epsilon algorithm, when applied to linearly generated vector sequences are Krylov subspace methods and it is known that they are equivalent to some well-known conjugate gradient type methods. However, the vector -algorithm is an extrapolation method, older than the four extrapolation methods above, and no similar results are known for it. In this paper, a determinantal formula for the vector -algorithm is given. Then it is shown that, when applied to a linearly generated vector sequence, the algorithm is also a Krylov subspace method and for a class of matrices the method is equivalent to a preconditioned Lanczos method. A new determinantal formula for the CGS is given, and an algebraic comparison between the vector -algorithm for linear systems and CGS is also given.