Chemical Bonding

The thesis is: the “periodic table” of “dark matter” is equivalent to the standard periodic table of the visible matter being entangled. Thus, it is to consist of all possible entangled states of the atoms of chemical elements as quantum systems. In other words, an atom of any chemical element and as a quantum system, i.e. as a wave function, should be represented as a non-orthogonal in general (i.e. entangled) subspace of the separable complex Hilbert space relevant to the system (...) to which the atom at issue is related as a true part of it. The paper follows previous publications of mine stating that “dark matter” and “dark energy” are projections of arbitrarily entangled states on the cognitive “screen” of Einstein’s “Mach’s principle” in general relativity postulating that gravitational field can be generated only by mass or energy. (shrink)

Van Inwagen proposes that besides simples only living organisms exist as composite objects. This paper suggests expanding van Inwagen’s ontology by also accepting composite objects in the case that physical bonding occurs (plus some extra conditions). Such objects are not living organ-isms but rather physical bodies. They include (approximately) the complete realm of inanimate ordinary objects, like rocks and tables, as well as inanimate scientific objects, like atoms and mol-ecules, the latter filling the ontological gap between simples and organisms in (...) van Inwagen’s origi-nal picture. We thus propose a compositional pluralism claiming that composition arises if and on-ly if bonding or life occurs. (shrink)

A modern version of Lewis’s theory of valency is presented. This takes account of the results of quantum–mechanical calculations on molecules. Topics covered are polar covalent bonds, hypervalency, coordinate bonds, nonintegral bonds, oxo-anions, variable valency among transition elements, and nonclassical compounds. A distinction is drawn between the valence shell of an atom and the Lewis shell. The concept of a fractional bond pair is presented.

Developments in the application of quantum mechanics to the understanding of the chemical bond are traced with a view to examining the evolving conception of the covalent bond. Beginning with the first quantum mechanical resolution of the apparent paradox in Lewis’s conception of a shared electron pair bond by Heitler and London, the ensuing account takes up the challenge molecular orbital theory seemed to pose to the classical conception of the bond. We will see that the threat of delocalisation can (...) be overstated, although it is questionable whether this should be seen as reinstating the issue of the existence of the chemical bond. More salient are some recent developments in a longstanding discussion of how to understand the causal aspects of the bonding interaction—the nature of the force involved in the covalent link—which are taken up in the latter part of the paper. (shrink)

The concepts of atoms and bonds in molecules which appeared in chemistry during the nineteenth century are unavoidable to explain the structure and the reactivity of the matter at a chemical level of understanding. Although they can be criticized from a strict reductionist point of view, because neither atoms nor bonds are observable in the sense of quantum mechanics, the topological and statistical interpretative approaches of quantum chemistry (quantum theory of atoms in molecules, electron localization function and maximum probability domain) (...) provide consistent definitions which accommodate chemistry and quantum mechanics. (shrink)

The status of the chemical bond has long been a controversial issue with the increasing distance between quantum chemists’ theoretical understanding of molecular stability and the ideas of experimental chemists. Some aspects of the development of the concept of a hydrogen bond are discussed with a view to assessing its import on the general question.

Summary Linus Pauling played a key role in creating valence-bond theory, one of two competing theories of the chemical bond that appeared in the first half of the 20th century. While the chemical community preferred his theory over molecular-orbital theory for a number of years, valence-bond theory began to fall into disuse during the 1950s. This shift in the chemical community's perception of Pauling's theory motivated Pauling to defend the theory, and he did so in a peculiar way. Rather than (...) publishing a defence of the full theory in leading journals of the day, Pauling published a defence of a particular model of the double bond predicted by the theory in a revised edition of his famous textbook, The Nature of the Chemical Bond. This paper explores that peculiar choice by considering both the circumstances that brought about the defence and the mathematical apparatus Pauling employed, using new discoveries from the Ava Helen and Linus Pauling Papers archive. (shrink)

It is argued that some elusive “entropic” characteristics of chemical bonds, e.g., bond multiplicities (orders), which connect the bonded atoms in molecules, can be probed using quantities and techniques of Information Theory (IT). This complementary perspective increases our insight and understanding of the molecular electronic structure. The specific IT tools for detecting effects of chemical bonds and predicting their entropic multiplicities in molecules are summarized. Alternative information densities, including measures of the local entropy deficiency or its displacement relative to the (...) system atomic promolecule, and the nonadditive Fisher information in the atomic orbital resolution(called contragradience) are used to diagnose the bonding patterns in illustrative diatomic and polyatomic molecules. The elements of the orbital communication theory of the chemical bond are briefly summarized and illustrated for the simplest case of the two-orbital model. The information-cascade perspective also suggests a novel, indirect mechanism of the orbital interactions in molecular systems, through “bridges” (orbital intermediates), in addition to the familiar direct chemical bonds realized through “space”, as a result of the orbital constructive interference in the subspace of the occupied molecular orbitals. Some implications of these two sources of chemical bonds in propellanes, π-electron systems and polymers are examined. The current–density concept associated with the wave-function phase is introduced and the relevant phase-continuity equation is discussed. For the first time, the quantum generalizations of the classical measures of the information content, functionals of the probability distribution alone, are introduced to distinguish systems with the same electron density, but differing in their current(phase) composition. The corresponding information/entropy sources are identified in the associated continuity equations. (shrink)

This treatise presents thoughts on the divide that exists in chemistry between those who seek their understanding within a universe wherein the laws of physics apply and those who prefer alternative universes wherein the laws are suspended or ‘bent’ to suit preconceived ideas. The former approach is embodied in the quantum theory of atoms in molecules (QTAIM), a theory based upon the properties of a system’s observable distribution of charge. Science is experimental observation followed by appeal to theory that, upon (...) occasion, leads to new experiments. This is the path that led to the development of the molecular structure hypothesis—that a molecule is a collection atoms with characteristic properties linked by a network of bonds that impart a structure—a concept forged in the crucible of nineteenth century experimental chemistry. One hundred and fifty years of experimental chemistry underlie the realization that the properties of some total system are the sum of its atomic contributions. The concept of a functional group, consisting of a single atom or a linked set of atoms, with characteristic additive properties forms the cornerstone of chemical thinking of both molecules and crystals and Dalton’s atomic hypothesis has emerged as the operational theory of chemistry. We recognize the presence of a functional group in a given system and predict its effect upon the static, reactive and spectroscopic properties of the system in terms of the characteristic properties assigned to that group. QTAM gives physical substance to the concept of a functional group. (shrink)

Heisenberg’s explanation of how two coupled oscillators exchange energy represented a dramatic success for his new matrix mechanics. As matrix mechanics transmuted into wave mechanics, resulting in what Heisenberg himself described as …an extraordinary broadening and enrichment of the formalism of the quantum theory , the term resonance also experienced a corresponding evolution. Heitler and London’s seminal application of wave mechanics to explain the quantum origins of the covalent bond, combined with Pauling’s characterization of the effect, introduced resonance into the (...) chemical lexicon. As the Valence Bond approach gave way to a soon-to-be dominant Molecular Orbital method, our understanding of the term resonance, as it might apply to our understanding the chemical bond, has also changed. (shrink)

Because most chemical reactions, by definition, cannot avoid breaking of bonds, weakly bonded species exist fleetingly in almost every chemical change. Historically, chemical quantum mechanics was aimed at explaining the nature of strong bonds. The theory involved a number of approximations to the full solution of the Schrödinger equation. The study of non‐Kekulé molecules provides an opportunity to test whether modern quantum chemical computations are competent to deal with the nature of molecules with very weak bonds. †To contact the author, (...) please write to: Department of Chemistry, Yale University, New Haven, CT: 06520‐8107; e‐mail: [email protected]. (shrink)

The wave-mechanical treatment of the valence bond, by Walter Heitler and Fritz London, and its ensuing foundational importance in quantum chemistry has been traditionally regarded as the basis for the argument that chemistry may be theoretically reduced to physics. Modern analyses of the reductionist claim focuses on the limitations to achieving full reduction in practice because of the approximations used in modern quantum chemical methods, but neglect the historical importance of the chemical bond as a chemical entity. This paper re-examines (...) these arguments with a study of the development of the valence bond by chemist Gilbert Lewis within a chemically autonomous framework, and its extension by Linus Pauling using Heitler and London’s methods. Here, we see that the chemical bond is best described as a theoretical synthesis or physico-chemical entity, to represent its full interdisciplinary importance from the philosophical and historical perspectives.Keywords: Reductionism; Chemical bond; Linus Pauling; Gilbert Lewis; Heitler–London; Chemical. (shrink)

In this article I sketch G. N. Lewis’s views on chemical bonding and Linus Pauling’s attempt to preserve Lewis’s insights within a quantum‐mechanical theory of the bond. I then set out two broad conceptions of the chemical bond, the structural and the energetic views, which differ on the extent in which they preserve anything like the classical chemical bond in the modern quantum‐mechanical understanding of molecular structure. †To contact the author, please write to: Department of Philosophy, Durham University, 50 Old (...) Elvet, Durham DH1 3HN, UK; e‐mail: [email protected]. (shrink)

Weisberg’s recent paper on the chemical bond makes the claim that the chemical notion of the covalent bond is in trouble. This note casts doubts on that claim.

Two different models for chemical bond were developed almost simultaneously after the Schrödinger formulation of quantum theory. These are known as the valence bond (VB) and molecular orbital (MO) theories. Initially chemists preferred the VB theory and ignored the MO theory. Now the VB theory is almost dropped out of currency. The context of discovery and Linus Pauling’s overpowering influence gave the VB theory its initial advantage. The current universal acceptance of the MO theory is due to its ability to (...) provide direct interpretation of many different types of experiments now being pursued. In current research both localized bonds and delocalized charge distributions play important roles and the MO theory has been successful in giving a good account of both. (shrink)

The covalent bond, a difficult concept to define precisely, plays a central role in chemical predictions, interventions, and explanations. I investigate the structural conception of the covalent bond, which says that bonding is a directional, submolecular region of electron density, located between individual atomic centers and responsible for holding the atoms together. Several approaches to constructing molecular models are considered in order to determine which features of the structural conception of bonding, if any, are robust across these models. Key components (...) of the structural conception are absent in all but the simplest quantum mechanical models of molecular structure, seriously challenging the conception’s viability. †To contact the author, please write to: Department of Philosophy, University of Pennsylvania, 433 Cohen Hall, Philadelphia, PA 19104‐6304; e‐mail: [email protected]. (shrink)

It is argued that the conventional descriptions of chemical bonds as covalent, ionic, metallic, and Van der Waals are compromising the usefulness of quantum mechanics in the synthesis and design of new molecules and materials. Parallels are drawn between the state of chemistry now and when the idea that phlogiston was an element impeded the development of chemistry. Overcoming the current obstacles will require new methods to describe molecular structure and bonding, just as new concepts were needed before the phlogiston (...) theory could be set aside. (shrink)

The London mathematical practitioner Henry Bond correctly forecast in The Sea-Mans Kalendar for 1636 [?1638] that the then easterly magnetic declination in London would become zero in 1657 and would then increase westerly for 'at least 30 years'. In 1668, he published a table of predicted changes in annual declination for the years 1668-1716. Despite a detailed examination of his later claim to be able to determine longitude using a dip needle, the basis for his earlier forecasts was not examined (...) and Bond himself appears never to have fully revealed his methods. It is demonstrated that Bond's predictions of 1636 and 1668 are consistent with the fitting of quadratic and cubic equations to existing observational data by means of the solution of simultaneous equations, and it is therefore argued that he anticipated 'Meyer's method' by over 100 years. Furthermore, Bond's forecast of 1668 made use of his discovery that the tangent of the angle of inclination is equal to twice the cotangent of the angle of magnetic latitude, thereby anticipating the findings of Biot and Krafft by c . 130 years. (shrink)

Most contemporary chemists consider quantum mechanics to be the foundational theory of their discipline, although few of the calculations that a strict reduction would seem to require have ever been produced. In this essay I discuss contemporary algebraic and diagrammatic representations of molecular systems derived from quantum mechanical models, specifically configuration interaction wavefunctions for ab initio calculations and molecular orbital energy diagrams. My aim is to suggest that recent dissatisfaction with reductive accounts of chemical theory may stem from both the (...) inability of standard accounts of reduction to incorporate the diverse forms of representation found in chemical practice and our philosophical predilection to analyze all connections between theories in terms of logical reduction. (shrink)

As timely renovation of artificial ideology about authenticity of nature in proportion to contemporaneous historical background of remarkable highlight of microcosmic configuration of matter, “Homogenous Cosmos Originated from Unique Genesis” is innovative cosmos redefinition and thoroughly coherent PNT dynamics about universal existence & motion as spontaneous occurrence in the nature of essence of matter in a class by itself, which is radically extended from newly highlighted factuality that “discretionary particles in cosmos are mutually convertible” as lineal logic system based on (...) unique assumable precondition of Homogenous cosmos originated from unique genesis postulate. (shrink)