Active set algorithms for isotonic regression; A unifying framework

In this and subsequent papers we will show that several algorithms for the isotonic regression problem may be viewed as active set methods. The active set approach provides a unifying framework for studying algorithms for isotonic regression, simplifies the exposition of existing algorithms and leads to several new efficient algorithms. We also investigate the computational complexity of several algorithms.In this paper we consider the isotonic regression problem with respect to a complete order where eachw _i is strictly positive and eachy _i is an arbitrary real number. We show that the Pool Adjacent Violators algorithm (due to Ayer et al., 1955; Miles, 1959; Kruskal, 1964), is a dual feasible active set method and that the Minimum Lower Set algorithm (due to Brunk et al., 1957) is a primal feasible active set method of computational complexity O(n ²). We present a new O(n) primal feasible active set algorithm. Finally we discuss Van Eeden's method and show that it is of worst-case exponential time complexity.This work was supported by the National Science and Engineering Research Council of Canada under Research Grant A8189 and an Ontario Graduate Scholarship.     

A theoretical approximation scheme for Stackelberg problems

We consider the Stackelberg problem corresponding to a two-player game in which one of the two players has the leadership in playing the game. We present a general approach for approximating the considered hierarchical programming problem by a sequence of two-level optimization problems. From a practical point of view, we also give some results for asymptotically Stackelberg approximating sequences and for problems with perturbed constraints.This paper is based upon results first presented at Journées Fermat: Mathematics for Optimization, Toulouse, France, May 1985.     

Relativistic atomic natural orbital type basis sets for the alkaline and alkaline-earth atoms applied to the ground-state potentials for the corresponding dimers

New basis sets of the atomic natural orbital (ANO) type have been developed for the atoms Li–Fr and Be–Ra. The ANOs have been obtained from the average density matrix of the ground states and the lowest excited states of the atom, the positive ion, and the dimer at its equilibirium geometry. Scalar realtivisitc effects are included through the use of a Douglas–Kroll Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of the ground-state potentials for the dimers. Computed bond energies are accurate to within 0.05 eV for the alkaline dimers and 0.02 eV for the alkaline-earth dimers (except for Be₂).Acknowledgments.ensp;B.O.R. would like to express his gratitude to Prof. Jacopo Tomasi for all the inspiration that his scientific work has given him through the years and continues to do in particular through the work on solvent effects on molecular properties. This work has been supported by a grant from the Swedish Science Research Council, VR.Contribution to the Jacopo Tomasi Honorary Issue     

Accurate Gaussian basis sets for the H2O molecule generated with the molecular improved generator coordinate Hartree–Fock method

The molecular improved generator coordinate Hartree–Fock (MIGCHF) method is used to generate accurate basis sets of primitive Gaussian-type functions for the H₂O molecule. Sequences of increasing size atom centered basis sets are employed to explore the accuracy that can be achieved with this method. Using the O(24s14p8d5f2g1h);H(22s9p5d2f1g) basis set, the HF and second-order electron correlation energies of the H₂O ground state at the experimental geometry are computed as −76.0674680 and −0.3491935 hartree, respectively. The HF energy is in error by 20 μhartree and the second-order correlation energy corresponds to 96.5% of an estimate of the limiting value. The relevance of the present calculations is to show the accuracy that can be achieved in studies of small polyatomic molecules with the MIGCHF method.     

Gaussian basis sets for calculation of spin densities in first-row atoms

Summary The suitability of Gaussian basis sets for ab initio calculation of Fermi contact spin densities is established by application to the prototype first-row atoms B-F having open shell p electrons. Small multiconfiguration self-consistent-field wave functions are used to describe relevant spin and orbital polarization effects. Basis sets are evaluated by comparing the results to highly precise numerical grid calculations previously carried out with the same wave function models. It is found that modest contracted Gaussian basis sets developed primarily for Hartree-Fock calculations can give semiquantitative results if augmented by diffuse functions and if further uncontracted in the outer core-inner valence region.     

Oxidative addition of the ethane C-C bond to Pd. An ab initio benchmark and DFT validation study

We have computed a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the ethane C-C bond to the palladium atom and have used this to evaluate the performance of 24 popular density functionals, covering LDA, GGA, meta-GGA, and hybrid density functionals, for describing this reaction. The ab initio benchmark is obtained by exploring the PES using a hierarchical series of ab initio methods [HF, MP2, CCSD, CCSD(T)] in combination with a hierarchical series of five Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Our best estimate of kinetic and thermodynamic parameters is -10.8 (-11.3) kcal/mol for the formation of the reactant complex, 19.4 (17.1) kcal/mol for the activation energy relative to the separate reactants, and -4.5 (-6.8) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). Our work highlights the importance of sufficient higher angular momentum polarization functions for correctly describing metal-d-electron correlation. Best overall agreement with our ab initio benchmark is obtained by functionals from all three categories, GGA, meta-GGA, and hybrid DFT, with mean absolute errors of 1.5 to 2.5 kcal/mol and errors in activation energies ranging from -0.2 to -3.2 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with a slight underestimation of the overall barrier by -0.9 kcal/mol. For comparison, with B3LYP we arrive at an overestimation of the overall barrier by 5.8 kcal/mol. On the other hand, B3LYP performs excellently for the central barrier (i.e., relative to the reactant complex) which it underestimates by only -0.1 kcal/mol.     

基于CAE仿真的行星齿轮减速器行星齿轮载荷分布特性研究

研究一种高效精确求解行星齿轮系统,在有误差情况下系统的不均载力学特性。应用有限元软件ABAQUS的PYTHON参数化设计语言,对含有5个行星齿轮的新能源汽车行星齿轮减速器,进行齿轮系统基于六面体网格单元的的参数化有限元建模;利用非线性接触分析方法求解减速器系统在有零部件制造和装配误差情况下,分析系统中行星齿轮的载荷分布特性,包括误差大小对不均载的影响,太阳轮输入载荷对不均载的影响。有限元分析结果与参考文献中的试验结果具有完全一致的结论,从而证明了分析方法的正确性。所提供的方法可以方便求解行星齿轮传动系统的不均载系数,对提高行星齿轮设备整机传动性能、寿命及新产品开发具有重要意义。     

Oriented hypergraphs: Balanceability

An oriented hypergraph is an oriented incidence structure that extends the concepts of signed graphs, balanced hypergraphs, and balanced matrices. We introduce hypergraphic structures and techniques that generalize the circuit classification of the signed graphic frame matroid to any oriented hypergraphic incidence matrix via its locally-signed-graphic substructure. To achieve this, Camion's algorithm is applied to oriented hypergraphs to provide a generalization of reorientation sets and frustration that is only well-defined on balanceable oriented hypergraphs. A simple partial characterization of unbalanceable circuits extends the applications to representable matroids demonstrating that the difference between the Fano and non-Fano matroids is one of balance.