A look at bonds and bonding

Structural Chemistry - Even after roughly a century of quantum theory, there is still debate, sometimes rather contentious, as to the nature of the chemical bond—or is it bonds, or is it...     

Electrostatics and Polarization in σ- and π-Hole Noncovalent Interactions: An Overview

The energetics of σ- and π-hole interactions can be described very well in terms of electrostatics and polarization, consistent with their Coulombic natures. When both of these components are taken into account, very good correlations with quantum-chemically computed interaction energies are obtained. If polarization is only minor, as when the interactions are quite weak, then electrostatics can suffice, as represented by the most positive electrostatic potential associated with the σ- or π-hole. For stronger interactions, the combination of electrostatics plus polarization is very effective even for interaction energies considerably greater in magnitude than what is normally considered noncovalent bonding. Several procedures for treating polarization are summarized, including the use of point charges and the direct inclusion of electric fields.     

On error bounds for lower semicontinuous functions

We give some sufficient conditions for proper lower semicontinuous functions on metric spaces to have error bounds (with exponents). For a proper convex function f on a normed space X the existence of a local error bound implies that of a global error bound. If in addition X is a Banach space, then error bounds can be characterized by the subdifferential of f. In a reflexive Banach space X, we further obtain several sufficient and necessary conditions for the existence of error bounds in terms of the lower Dini derivative of f. Received: April 27, 2001 / Accepted: November 6, 2001?Published online April 12, 2002     

Necessary and sufficient optimality conditions for mathematical programs with equilibrium constraints

In this paper we consider a mathematical program with equilibrium constraints (MPEC) formulated as a mathematical program with complementarity constraints. Various stationary conditions for MPECs exist in literature due to different reformulations. We give a simple proof to the M-stationary condition and show that it is sufficient for global or local optimality under some MPEC generalized convexity assumptions. Moreover, we propose new constraint qualifications for M-stationary conditions to hold. These new constraint qualifications include piecewise MFCQ, piecewise Slater condition, MPEC weak reverse convex constraint qualification, MPEC Arrow-Hurwicz-Uzawa constraint qualification, MPEC Zangwill constraint qualification, MPEC Kuhn-Tucker constraint qualification, and MPEC Abadie constraint qualification.     

A Class of Quadratic Programs with Linear Complementarity Constraints

We consider a class of quadratic programs with linear complementarity constraints (QPLCC) which belong to mathematical programs with equilibrium constraints (MPEC). We investigate various stationary conditions and present new and strong necessary and sufficient conditions for global and local optimality. Furthermore, we propose a Newton-like method to find an M-stationary point in finite steps without MEPC linear independence constraint qualification. The research of this author is partially supported by NSERC, and Research Grand Council of Hong Kong.     

Enhanced Karush–Kuhn–Tucker condition and weaker constraint qualifications

In this paper we study necessary optimality conditions for nonsmooth optimization problems with equality, inequality and abstract set constraints. We derive the enhanced Fritz John condition which contains some new information even in the smooth case than the classical enhanced Fritz John condition. From this enhanced Fritz John condition we derive the enhanced Karush–Kuhn–Tucker condition and introduce the associated pseudonormality and quasinormality condition. We prove that either pseudonormality or quasinormality with regularity on the constraint functions and the set constraint implies the existence of a local error bound. Finally we give a tighter upper estimate for the Fréchet subdifferential and the limiting subdifferential of the value function in terms of quasinormal multipliers which is usually a smaller set than the set of classical normal multipliers. In particular we show that the value function of a perturbed problem is Lipschitz continuous under the perturbed quasinormality condition which is much weaker than the classical normality condition.