Non‐empirical calculations of NMR indirect carbon–carbon coupling constants. Part 4: Bicycloalkanes

A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd.     

Propriétés statistiques des entiers friables

Let Ψ(x,y) (resp. Ψ_m(x,y)) denote the number of integers not exceeding x that are y-friable, i.e. have no prime factor exceeding y (resp. and are coprime to m). Evaluating the ratio Ψ_m(x/d,y)/Ψ(x,y) for 1≤slantd≤slantx, m≥slant 1, x≥slant y≥slant 2, turns out to be a crucial step for estimating arithmetic sums over friable integers. Here, it is crucial to obtain formulae with a very wide range of validity. In this paper, several uniform estimates are provided for the aforementioned ratio, which supersede all previously known results. Applications are given to averages of various arithmetic functions over friable integers which in turn improve corresponding results from the literature. The technique employed rests mainly on the saddle-point method, which is an efficient and specific tool for the required design.2000 Mathematics Subject Classification: Primary—11N25; Secondary—11K65, 11N37     

A note on strong β-I-sets and strongly β-I-continuous functions

Summary In [6], we introduced and investigated the notions of strong β-I-open sets and strong β-I-continuous functions in ideal topological spaces. In this paper, we investigate further their important properties.     

Local Feasible QP-Free Algorithms for the Constrained Minimization of SC1 Functions

We consider the problem of minimizing an SC¹ function subject to inequality constraints. We propose a local algorithm whose distinguishing features are that: (a) a fast convergence rate is achieved under reasonable assumptions that do not include strict complementarity at the solution; (b) the solution of only linear systems is required at each iteration; (c) all the points generated are feasible. After analyzing a basic Newton algorithm, we propose some variants aimed at reducing the computational costs and, in particular, we consider a quasi-Newton version of the algorithm.     

On the spectral norm of algebraic numbers

In this paper we continue to study the spectral norms and their completions ([4]) in the case of the algebraic closure $ \overline {\mathbb Q} $ of ? in ?. Let $ \widetilde{\overline{\mathbb{Q}}} $ be the completion of $ \overline {\mathbb Q} $ relative to the spectral norm. We prove that $ \widetilde{\overline{\mathbb{Q}}} $ can be identified with the R‐subalgebra of all symmetric functions of C(G), where C(G) denotes the ?‐Banach algebra of all continuous functions defined on the absolute Galois group G = Gal$ {\overline {\mathbb Q}} / {\mathbb Q} $. We prove that any compact, closed to conjugation subset of ? is the pseudo‐orbit of a suitable element of $ \widetilde{\overline{\mathbb{Q}}} $. We also prove that the topological closure of any algebraic number field in $ \widetilde{\overline{\mathbb{Q}}} $ is of the form $\widetilde{\mathbb{Q}[x]}$ with x in $ \widetilde{\overline{\mathbb{Q}}} $.     

Resolution of Some Open Problems Concerning Multiple Zeta Evaluations of Arbitrary Depth

We prove some new evaluations for multiple polylogarithms of arbitrary depth. The simplest of our results is a multiple zeta evaluation one order of complexity beyond the well-known Broadhurst–Zagier formula. Other results we provide settle three of the remaining outstanding conjectures of Borwein, Bradley, and Broadhurst. A complete treatment of a certain arbitrary depth class of periodic alternating unit Euler sums is also given.     

The Gram Matrix of a PT-Symmetric Quantum System

The eigenstates of a diagonalizable PT-symmetric Hamiltonian satisfy unconventional completeness and orthonormality relations. These relations reflect the properties of a pair of bi-orthonormal bases associated with non-hermitean diagonalizable operators. In a similar vein, such a dual pair of bases is shown to possess, in the presence of PT symmetry, a Gram matrix of a particular structure: its inverse is obtained by simply swapping the signs of some its matrix elements.     

Fixed points in the family of convex representations of a maximal monotone operator

Any maximal monotone operator can be characterized by a convex function. The family of such convex functions is invariant under a transformation connected with the Fenchel-Legendre conjugation. We prove that there exists a convex representation of the operator which is a fixed point of this conjugation.

     

Cyclic Hypomonotonicity,Cyclic Submonotonicity,and Integration

Rockafellar has shown that the subdifferentials of convex functions are always cyclically monotone operators. Moreover, maximal cyclically monotone operators are necessarily operators of this type, since one can construct explicitly a convex function, which turns out to be unique up to a constant, whose subdifferential gives back the operator. This result is a cornerstone in convex analysis and relates tightly convexity and monotonicity. In this paper, we establish analogous robust results that relate weak convexity notions to corresponding notions of weak monotonicity, provided one deals with locally Lipschitz functions and locally bounded operators. In particular, the subdifferentials of locally Lipschitz functions that are directionally hypomonotone [respectively, directionally submonotone] enjoy also an additional cyclic strengthening of this notion and in fact are maximal under this new property. Moreover, every maximal cyclically hypomonotone [respectively, maximal cyclically submonotone] operator is always the Clarke subdifferential of some directionally weakly convex [respectively, directionally approximately convex] locally Lipschitz function, unique up to a constant, which in finite dimentions is a lower C² function [respectively, a lower C¹ function].     

Harnack inequality for some classes of Markov processes

In this paper we establish a Harnack inequality for nonnegative harmonic functions of some classes of Markov processes with jumps. Mathematics Subject Classification (2000): Primary 60J45, 60J75, Secondary 60J25.This work was completed while the authors were in the Research in Pairs program at the Mathematisches Forschungsinstitut Oberwolfach. We thank the Institute for the hospitality.The research of this author is supported in part by NSF Grant DMS-9803240.The research of this author is supported in part by MZT grant 0037107 of the Republic of Croatia.