Electron-pairing analysis from localization and delocalization indices in the framework of the atoms-in-molecules theory

This article presents an overview of recent advances in the study of electron pairing through the use of localization and delocalization indices obtained from double integration over atomic basins of the exchange–correlation density in the framework of the atoms-in-molecules theory. These localization and delocalization indices describe the intra- and interatomic distribution of the electron pairs in a molecule. The main results of the application of these second-order indices to the analysis of molecular structure and chemical reactivity are briefly reviewed. It is shown that localization and delocalization indices represent a powerful tool to describe the electron-pair structure of molecules, which, in turn, provides deeper insight into relevant chemical phenomena such as electron correlation effects and the formation of localized α, β electron pairs. Received: 8 April 2002 / Accepted: 26 June 2002 / Published online: 6 September 2002 Acknowledgements. Financial help was furnished by the Spanish DGES projects no. PB98-0457-C02-01 and BQU2002-04112-C02-02. J.P. thanks the Departament d'Universitats, Recerca i Societat de la Informació de la Generalitat de Catalunya for benefiting from a doctoral fellowship, no. 2000FI-00582. M.S. is indebted to the Departament d'Universitats, Recerca i Societat de la Informació of the Generalitat de Catalunya for financial support through the Distinguished University Research Promotion, 2001. We also thank the Centre de Supercomputació de Catalunya for providing us with computing facilities. Correspondence to: M. Solà e-mail: miquel.sola@udg.es     

A Remark on the Fourier Pairing and the Binomial Formula for the Macdonald Polynomials

We concisely and directly prove that the interpolation Macdonald polynomials are orthogonal with respect to the Fourier pairing and briefly discuss immediate applications of this fact, in particular, to the symmetry of the Fourier pairing and to the binomial formula.     

Cutting and Surrogate Constraint Analysis for Improved Multidimensional Knapsack Solutions

We use surrogate analysis and constraint pairing in multidimensional knapsack problems to fix some variables to zero and to separate the rest into two groups – those that tend to be zero and those that tend to be one, in an optimal integer solution. Using an initial feasible integer solution, we generate logic cuts based on our analysis before solving the problem with branch and bound. Computational testing, including the set of problems in the OR-library and our own set of difficult problems, shows our approach helps to solve difficult problems in a reasonable amount of time and, in most cases, with a fewer number of nodes in the search tree than leading commercial software.     

Spatial,Hysteretic, and Adaptive Host–Guest Chemistry in a Metal–Organic Framework with Open Watson–Crick Sites

Biological and artificial molecules and assemblies capable of supramolecular recognition, especially those with nucleobase pairing, usually rely on autonomous or collective binding to function. Advanced site‐specific recognition takes advantage of cooperative spatial effects, as in local folding in protein–DNA binding. Herein, we report a new nucleobase‐tagged metal–organic framework (MOF), namely ZnBTCA (BTC=benzene‐1,3,5‐tricarboxyl, A=adenine), in which the exposed Watson–Crick faces of adenine residues are immobilized periodically on the interior crystalline surface. Systematic control experiments demonstrated the cooperation of the open Watson–Crick sites and spatial effects within the nanopores, and thermodynamic and kinetic studies revealed a hysteretic host–guest interaction attributed to mild chemisorption. We further exploited this behavior for adenine–thymine binding within the constrained pores, and a globally adaptive response of the MOF host was observed.     

Responsive Copolymer Brushes of Poly[(2‐(Methacryloyloxy)Ethyl) Trimethylammonium Chloride] (PMETAC) and Poly(1H,1H,2H,2H‐Perfluorodecyl acrylate) (PPFDA) to Modulate Surface Wetting Properties

Polymer brushes have a large potential for controlling properties such as surface lubrication or wetting through facile functionalization. Polymer chemistry, chain density, and length impact on the wetting properties of brushes. This study explores the use of diblock copolymer brushes with different block length and spatial arrangement of the blocks to tune surface wettability. Block copolymer brushes of the polyelectrolyte [2‐(methacryloyloxy)ethyl] trimethylammonium chloride (PMETAC) with a contact angle of 17° and a hydrophobic block of ¹H, ¹H, ²H, ²H‐perfluorodecyl Acrylate (PPFDA) with a contact angle of 130° are synthesized by RAFT polymerization. By changing the sequence of polymerization either block is synthesized as top or bottom block. By varying the concentration of initiator the length of the blocks is varied. Contact angle values with intermediate values between 17° and 130° are measured. In addition, by changing solvent pH and in presence of a different salt the contact angle of the copolymer brushes can be fine tuned. Brushes are characterized by atomic force microscopy, Raman confocal microscopy, and X‐ray photoelectron spectroscopy.

     

Extremely localized nonorthogonal orbitals by the pairing theorem

Using the concepts of L?wdin pairing theorem, a method is developed to calculate extremely localized, but nonorthogonal, sets of molecular orbitals and their strictly localized counterparts. The method is very suitable to study to what extent a given model of bonding in a given molecule can be considered adequate from the point of view of the actual LCAO-MO (Hartree Fock or DFT) wave function and is expected to be useful for doing local approximations of electron correlation.     

Simple monadic theories and indiscernibles

Aiming for applications in monadic second‐order model theory, we study first‐order theories without definable pairing functions. Our main results concern forking‐properties of sequences of indiscernibles. These turn out to be very well‐behaved for the theories under consideration (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

An extension of the pairing theory between divergence-measure fields and BV functions

In this paper we introduce a nonlinear version of the notion of Anzellotti's pairing between divergence-measure vector fields and functions of bounded variation, motivated by possible applications to evolutionary quasilinear problems. As a consequence of our analysis, we prove a generalized Gauss–Green formula.     

Resultants and the algebraicity of the join pairing on Chow varieties

The Chow/Van der Waerden approach to algebraic cycles via resultants is used to give a purely algebraic proof for the algebraicity of the complex suspension. The algebraicity of the join pairing on Chow varieties then follows. The approach implies a more algebraic proof of Lawson's complex suspension theorem in characteristic 0. The continuity of the action of the linear isometries operad on the group completion of the stable Chow variety is a consequence.