The reaction force. A scalar property to characterize reaction mechanisms

The reaction force is a global property of a chemical reaction that arises when applying the Hellmann–Feynmann theorem to the potential energy surface that links reactants, products and transition states. In the present work, the reaction force is defined rigorously from the cartesian components coming out from all forces exerted over each atom of a molecular system during the chemical reaction; it is demonstrated that the reaction force is a scalar property. An erratum to this article can be found at     

Proof of the Fukui conjecture via resolution of singularities and related methods. II $$^{\star}$$

The present article is a direct continuation of the first part of this series. We reduce a proof of the Fukui conjecture (concerning the additivity problem of the zero-point vibrational energies of hydrocarbons) to that of a proposition related to the theory of algebraic curves, so that we can focus on the key mechanism of the additivity phenomena. Namely, by establishing what is called the Basic Piecewise Monotone Theorem (BPMT), we reduce a proof of the Fukui conjecture to that of a proposition, called the Local Analyticity Proposition, Version 1 (LAP1), which admits a proof via resolution of singularities. By LAP1, the essential part of the mechanism of the asymptotic linearity phenomena is extracted and is elucidated by using tools from the mathematical theory of algebraic curves, whose language is of vital importance in analyzing the crux of the additivity mechanism. Dedicated to the memory of Prof. Kenichi Fukui (1918–1998).     

On the role of localized molecular orbitals in the formation of bond dipoles

The hypothesis of the classical chemistry about bond dipoles resulting from shifts of separate pairs of electrons is proved using the non-canonical method of molecular orbitals (MOs). To this end, a relation is sought between the total charge distribution inside an individual chemical bond of a polyatomic molecule and the square of the respective single localized MO (LMO). General expressions for these MOs are obtained directly on the basis of the Brillouin theorem without invoking additional localization criteria. The two characteristics under comparison are presented in an explicit algebraic form in terms of meaningful components. Reshaping of square of the ‘own’ LMO of the given bond is shown to play the decisive role in the formation of secondary dipoles of initially homopolar bonds (e.g. of C–C and C–H bonds in substituted alkanes), as well as of bonds of relatively low initial polarity. Thus, representability of these dipoles by shifts of the ‘own’ pairs of electrons of respective bonds is supported. For bonds of a high initial polarity, the secondary dipoles are shown to originate mainly from contributions of LMOs of other bonds extending over the antibonding basis orbital of the given bond. Moreover, the actual secondary bond dipole takes an opposite direction vs. that predicted by the shift of the respective ‘own’ pair of electrons in this case. The latter result serves to account for the known low nucleofugality of highly electronegative heteroatoms in the S_N2 reactions.     

Repeat Space Theory Applied to Carbon Nanotubes and Related Molecular Networks. I

The present article is the first part of a series devoted to extending the Repeat Space Theory (RST) to apply to carbon nanotubes and related molecular networks. Four key problems are formulated whose affirmative solutions imply the formation of the initial investigative bridge between the research field of nanotubes and that of the additivity and other network problems studied and solved by using the RST. All of these four problems are solved affirmatively by using tools from the RST. The Piecewise Monotone Lemmas (PMLs) are cornerstones of the proof of the Fukui conjecture concerning the additivity problems of hydrocarbons. The solution of the fourth problem gives a generalized analytical formula of the pi-electron energy band curves of nanotube (a, b), with two new complex parameters c and d. These two parameters bring forth a broad class of analytic curves to which the PMLs and associated theoretical devices apply. Based on the above affirmative solutions of the problems, a central theorem in the RST, called the asymptotic linearity theorem (ALT) has been applied to nanotubes and monocyclic polyenes. Analytical formulae derived in this application of the ALT illuminate in a new global context (i) the conductivity of nanotubes and (ii) the aromaticity of monocyclic polyenes; moreover an analytical formula obtained by using the ALT provides a fresh insight into Hückel’s (4n+2) rule. The present article forms a foundation of the forthcoming articles in this series. The present series of articles is closely associated with the series of articles entitled ‘Proof of the Fukui conjecture via resolution of singularities and related methods’ published in the JOMC.     

An extension of Suffridge's convolution theorem

We present an extension of Suffridge's convolution theorem for polynomials with restricted zeros on the unit circle. We also discuss a possible extension of the theorem of Laguerre for those polynomials and give an answer to a long-standing open question by Suffridge regarding an extension of the theorem of Gauß-Lucas.     

Generalized Besov spaces and Triebel-Lizorkin spaces

In this paper the classical Besov spaces Bsp.q and Triebel-Lizorkin spaces Fsp.q for s ∈R are generalized in an isotropy way with the smoothness weights {|2j|aln}∞j=0. These generalized Besov spaces and Triebel-Lizorkin spaces, denoted by Bap.q and Fap.q for a ∈Irk and k ∈N, respectively, keep many interesting properties, such as embedding theorems (with scales property for all smoothness weights), lifting properties for all parameters a, and duality for index 0 < p < ∞. By constructing an example, it is shown that there are infinitely many generalized Besov spaces and generalized Triebel-Lizorkin spaces lying between Bs,p.q and ∪tsBt,p.q,and between Fsp.q and ∪ts Ftp.q, respectively. Between Bs,p,q and ∪tsBt,p.qq,and between Fsp,qand ∪tsFtp.q,respectively.     

Resplendent models and $${\Sigma_1^1}$$ -definability with an oracle

In this article we find some sufficient and some necessary -conditions with oracles for a model to be resplendent or chronically resplendent. The main tool of our proofs is internal arguments, that is analogues of classical theorems and model-theoretic constructions conducted inside a model of first-order Peano Arithmetic: arithmetised back-and-forth constructions and versions of the arithmetised completeness theorem, namely constructions of recursively saturated and resplendent models from the point of view of a model of arithmetic. These internal arguments are used in conjunction with Pabion’s theorem that ensures that certain oracles are coded in a sufficiently saturated model of arithmetic. Examples of applications are provided for the theories of dense linear orders and of discrete linear orders. These results are then generalised to other ω-categorical theories and theories with a unique countable recursively saturated model.      

Lagrange-type duality in DC programming

We show a Lagrange-type duality theorem for a DC programming problem, which is a generalization of previous results by J.-E. Martínez-Legaz, M. Volle [5] and Y. Fujiwara, D. Kuroiwa [1] when all constraint functions are real-valued. To the purpose, we decompose the DC programming problem into certain infinite convex programming problems.     

ALGEBRAIC EXTENSION OF ＊-A OPERATOR

In this paper, we study various properties of algebraic extension of *-A operator.Specifically, we show that every algebraic extension of *-A operator has SVEP and is isoloid.And if T is an algebraic extension of *-A operator, then Weyl's theorem holds for f(T), where f is an analytic functions on some neighborhood of σ(T) and not constant on each of the components of its domain.