Challenges to the Structural Conception of Chemical Bonding (original) (raw)

The chemical bond as an emergent phenomenon

The Journal of Chemical Physics, 2017

We first argue that the covalent bond and the various closed-shell interactions can be thought of as symmetry broken versions of one and the same interaction, viz., the multi-center bond. We use specially chosen molecular units to show that the symmetry breaking is controlled by density and electronegativity variation. We show that the bond order changes with bond deformation but in a step-like fashion, regions of near constancy separated by electronic localization transitions. These will often cause displacive transitions as well so that the bond strength, order, and length are established self-consistently. We further argue on the inherent relation of the covalent, closed-shell, and multi-center interactions with ionic and metallic bonding. All of these interactions can be viewed as distinct sectors on a phase diagram with density and electronegativity variation as control variables; the ionic and covalent/secondary sectors are associated with on-site and bond-order charge density wave respectively, the metallic sector with an electronic fluid. While displaying a contiguity at low densities, the metallic and ionic interactions represent distinct phases separated by discontinuous transitions at sufficiently high densities. Multi-center interactions emerge as a hybrid of the metallic and ionic bond that results from spatial coexistence of delocalized and localized electrons. In the present description, the issue of the stability of a compound is that of mutual miscibility of electronic fluids with distinct degrees of electron localization, supra-atomic ordering in complex inorganic compounds comes about naturally. The notions of electronic localization advanced hereby suggest a high throughput, automated procedure for screening candidate compounds and structures with regard to stability, without the need for computationally costly geometric optimization.

A commentary on Weisberg’s critique of the ‘structural conception’ of chemical bonding

Foundations of Chemistry

Robin Hendry has presented an account of two equally valid ways of understanding the nature of chemical bonding, consisting of what the terms the structural and the energetic views respectively. In response, Weisberg has issued a “challenge to the structural view”, thus implying that the energetic view is the more correct of the two conceptions. In doing so Weisberg identifies the delocalization of electrons as the one robust feature that underlies the increasingly accurate quantum mechanical calculations starting with the Heitler-London method and moving on to such approaches as the valence bond and molecular orbital theories of chemical bonding. The present article provides a critical evaluation of Weisberg’s article and concludes that he fails to characterize the nature of chemical bonding in several respects. I claim that Hendry’s structural and energetic views remain as equally viable ways of understanding chemical bonding. Whereas the structural view is more appropriate for ch...

Identifying Conceptions of the Covalent Bond: An Analysis from a Systematic Review

Química Nova

The covalent bond is a classical topic in science education because it is fundamental to a considerable number of other concepts and by its ability to interpret several chemical phenomena. However, the process of learning this concept presents some difficulties discussed here. This article brings together the conceptions related to the covalent bond, identified, and reported from other studies, to find similarities and to organize what is known about the topic in epistemological themes. In this paper, it was conducted a systematic review using 3 databases, reaching more than 200 reports, and classified 253 sentences of misconceptions in 7 epistemological themes. The main contribution of this article is the classification of misconceptions into themes, which enables teachers and researchers to easily identify a topic considering its complexity. This review shows different misconceptions over the same topic, how misinterpretations can appear over all the models and theories related to...

Bonds and Intermolecular Interactions – The Return of Cohesion to Chemistry

Intermolecular Interactions in Crystals: Fundamentals of Crystal Engineering

This chapter is a very brief historical tale of the evolution of the concept of “cohesion” in chemistry. This is done by overviewing the emergence of the bond concept that glues atoms into molecules, and of the intermolecular interactions that assemble molecules into larger aggregates of matter. By reviewing some novel bonding motifs and new aspects of intermolecular interactions, the chapter shows that the field of cohesion in chemistry is vibrant, exciting, and is teeming with problems awaiting solution. The imaging of bonds, bond breaking and remaking, and putatively of hydrogen bonds and maybe also of halogen bonds, in the future, mark the excitement of the community to probe these abstract concepts by experimental means. It is bonding time in chemistry!

Chemical bonding: state of the art in conceptual quantum chemistry An introduction

… , Computation, and Modeling (Theoretica Chimica Acta …, 2001

The de®nitive basis of a reductionistic explanation of chemistry, that is, of atomic bonding, of changes of bonding and of the emergence of macroscopic properties and their changes was established through the invention of quantum mechanics by Heisenberg, SchroÈ dinger and Dirac starting in 1925 and by the application of the nonrelativistic part of the theory by early quantum chemists. Nevertheless, the modern concepts of chemical bonding must account, on one hand at least, for the systematics found empirically in previous decades and

Is there any fundamental difference between ionic, covalent, and others types of bond? A canonical perspective on the question

Physical Chemistry Chemical Physics, 2017

The concept of chemical bonding is normally presented and simplified through two models: the covalent bond and the ionic bond. Expansion of the ideal covalent and ionic models leads chemists to the concepts of electronegativity and polarizability, and thus to the classification of polar and non-polar bonds. In addition, the intermolecular interactions are normally viewed as physical phenomena without direct correlation to the chemical bond in any simplistic model. Contrary to these traditional concepts of chemical bonding, recently developed canonical approaches demonstrate a unified perspective on the nature of binding in pairwise interatomic interactions. This new canonical model, which is a force-based approach with a basis in fundamental molecular quantum mechanics, confirms much earlier assertions that in fact there are not fundamental distinctions among covalent bonds, ionic bonds, and intermolecular interactions including the hydrogen bond, the halogen bond, and van der Waals interactions.

DOI 10.1007/s10698-013-9192-2 Atoms and bonds in molecules and chemical explanations

2013

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.