Although the electron density can be calculated with the formal resources of quantum mechanics, in physics it does not play the leading role that the quantum state does. In contrast, the concept of electron density is central in quantum chemistry. There is no doubt about how the electron density is computed in terms of the wave function of an atom or molecule. However, when the interpretation of the concept is at stake, there is no general agreement. In this article we (...) will analyze the two main interpretations of the concept of electron density: the Born-style probability density interpretation and the Schrödinger-style charge density interpretation. In particular, we will examine their differences, their relations with quantum mechanics and the consequences that each of them entails from a strictly quantum point of view. (shrink)

This article aims to clarify how aspects of current chemical understanding relate to some important contemporary problems of philosophy. The first section points out that the long-running philosophical debates concerning how properties stay together in substances have neglected the important topic of structure-determining closure. The second part describes several chemically-important types of closure and the third part shows how such closures ground the properties of chemical substances. The fourth section introduces current discussions of structural realism (SR) and contextual emergence: the (...) final sections reconsider the coherence of the properties of substances and concludes that recognition that structures qualify as determinants of specific outcomes—as ‘causes’ as that designation is used in Standard English—clarifies how properties stay together in chemical entities, and by analogy, how characteristics cohere in ordinary items. (shrink)

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 chemists, the energetic view is preferable to physicists. Neither view is more correct unless one subscribes to the naively reductionist view of considering that the more physical energetic view is the more correct one. (shrink)

This thesis investigates the epistemological and metaphysical relations between chemistry and quantum mechanics. These relations are examined with respect to how chemistry and quantum mechanics each describe a single inert molecule. A review of how these relations are understood in the literature shows that there is a proliferation of positions which focus on how chemistry is separate from quantum mechanics. This proliferation is accompanied by a tendency within the philosophy of chemistry community to connect the legitimacy of the field with (...) the autonomy of chemistry. First, it is argued that this connection should not be made. Secondly, it is argued that chemistry and quantum mechanics are unified in accordance with Harold Kincaid’s model of non-reductive unity because the two theories exhibit particular epistemic and metaphysical interconnections. Thirdly, a metaphysical account is examined which is incompatible with Kincaid’s model of unity; namely strong emergence as understood by Robin Hendry. According to Hendry, the structure of a single inert molecule strongly emerges from its quantum mechanical entities in the sense that there is downward causation. However, Hendry’s defense of this account faces certain problems. Moreover, the putative empirical evidence for his understanding of strong emergence can be explained without invoking strong emergence. This is shown by considering how quantum mechanics assumes an idealized understanding of a molecule’s stability and structure. In the light of the philosophical literature on idealizations, this idealization can be interpreted in two different ways, both of which explain why quantum mechanics describes the structure of a single molecule the way it does, without assuming strong emergence in Hendry’s sense. Each interpretation has philosophical implications regarding the nature of chemical properties, and the relation of chemistry and quantum mechanics. These implications are consistent with Kincaid’s model of unity and thus further support chemistry’s unity with quantum mechanics (as per Kincaid). (shrink)

Within quantum chemistry, the electron clouds that surround nuclei in atoms and molecules are sometimes treated as clouds of probability and sometimes as clouds of charge. These two roles, tracing back to Schrödinger and Born, are in tension with one another but are not incompatible. Schrödinger’s idea that the nucleus of an atom is surrounded by a spread-out electron charge density is supported by a variety of evidence from quantum chemistry, including two methods that are used to determine atomic and (...) molecular structure: the Hartree-Fock method and density functional theory. Taking this evidence as a clue to the foundations of quantum physics, Schrödinger’s electron charge density can be incorporated into many different interpretations of quantum mechanics. (shrink)

A novel non-classical mereological concept built up by blending the Metaphysics of Xavier Zubiri and the Quantum Theory of Atoms in Molecules of R. F. W. Bader is proposed. It is argued that this philosophical concept is necessary to properly account for what happens in a chemical reaction. From the topology of the gradient of the laplacian of the electronic charge density, \\) within the QTAIM framework, different “atomic graphs” are found for each atom depending on the molecular context, reflecting (...) how the whole molecule affects each atom. In this way, the whole molecular system imposes certain geometry onto each atom, and every atom exhibits different ontological modality. On the Metaphysical side, for X. Zubiri real things are system of different notes. The physical essence is the subsystem of essential notes with a coherence unity. Every note is grounded on the essence. The unity of the system is present somehow in every note-of beforehand, and every essential note-of turns towards the other. The essence determines the position of each note within the system, and hence is the grounding for modality of the notes. By conflating both “theories” and taking the atoms as essential notes, we propose the concept of “Molecule in atoms-of” or “atoms-of in Molecules”. Within the course of a chemical reaction the atoms-of modified their “of” as required by the new molecular unity being formed, and eventually change their modality. The validity to the Zubiri’s statements, is attained by evaluating necessity and possibility in a set-up of finite accessible “possible worlds”. (shrink)

The concept of molecular structure is one of the most important concepts of chemistry. In fact, molecular structure is closely related to the concept of chemical substance and its set of properties, and it is the main factor in the explanation of reactivity. In fact, much of the behavior of substances is explained in terms of the structure of their component molecules. This may explain why people tend to take the notion of molecular structure for granted. However, the problem begins (...) already when it comes to specifying the concept, since there is no clear definition of ‘molecular structure’ valid for all chemistry. The purpose of the present article is to show that the term ‘molecular structure’ subsumes very different notions, which depend on how the molecule and its components are conceived, and each of which brings its own difficulties. In particular, we will focus on how the molecule and its structure are devised from a classical view and from a quantum–mechanical view, and will discuss the different problems related with molecular structure that arise in each case. (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)

An Aristotelian philosophy of nature offers an alternative to reduction for the conception of the inter-theoretical relationships between molecular chemistry and quantum mechanics. A basic ingredient for such an approach is an ontology of fundamental causal powers, and this work aims to develop such an ontology by drawing on quantum-chemical entities, particularly, the electron density. This notion is central to the Quantum Theory of Atoms in Molecules, a theory of molecular structure developed by Richard F. W. Bader, which describes molecules (...) and atoms in terms precisely of the electron density. Then, by identifying a philosophical tension in Bader’s discourse about the nature of electron density, the work will analyze this central notion in terms of the categorical/dispositional distinction regarding properties. The central idea is that electron density can be conceived as categorical and dispositional at once, and this very characterization can avoid Bader’s philosophical tension. (shrink)

By moving away from the traditional reductionist reading of the quantum theory of atoms in molecules, in this paper we analyze the role played by QTAIM in the relationship between molecular chemistry and quantum mechanics from an emergentist perspective. In particular, we show that such a relationship involves two steps: an intra-domain emergence and an inter-domain emergence. Intra-domain emergence, internal to quantum mechanics, results from the fact that the electron density, from which all the other QTAIM’s concepts are defined, arises (...) from the wavefunction as a coarse-grained magnitude. Inter-domain emergence involves an analogical link, a mapping, between QTAIM’s entities, such as topological atoms and bond paths, and the entities that populate the molecular-chemistry domain, such as chemical atoms and chemical bonds. (shrink)

According to classical molecular chemistry, molecules have a structure, that is, they are sets of atoms with a definite arrangements in space and held together by chemical bonds. The concept of molecular structure is central to modern chemical thought given its impressive predictive power. It is also a very useful concept in chemistry education, due to its role in the rationalization and visualization of microscopic phenomena. However, such a concept seems to find no place in the ontology described by quantum (...) mechanics, since it appeals to classical notions such as the position of the atomic nuclei or the individuality of electrons. Although this problem has attracted the attention of several authors, the discussion is far from settled. Some authors adopt an explicitly reductionist position and advocate to reconstruct the concept of molecular structure within the framework of the quantum theory. Others, although acknowledging the conceptual discontinuity between quantum mechanics and molecular chemistry, keep the hope of future reduction alive. From an explicitly non-reductionist position, on the contrary, others authors conceive molecular structure as an emergent phenomenon. The purpose of this article is to propose a different line of argumentation to address this problem. By contrast to reduction and emergence, the admission of a multiplicity of ontologies, not necessarily linked by hierarchical connections, cancels the need of finding a relation of dependence between the molecular level and the quantum level. This ontologically pluralist position can be applied to the issue of molecular structure, in order to argue that it is possible to admit the existence of structure in the ontology of molecular chemistry, in spite of the fact that it does not exist in the quantum world. (shrink)