In this paper we will address the problem of the existence of orbitals by analyzing the relationship between molecular chemistry and quantum mechanics. In particular, we will consider the concept of orbital in the light of the arguments that deny its referring character. On this basis, we will conclude that the claim that orbitals do not exist relies on a metaphysical reductionism which, if consistently sustained, would lead to consequences clashing with the effective practice of science in its different branches.

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)

I present a response to Vollmer's review of the book Of Minds and Molecules, and especially her comments on my own article therein. This provides an opportunity to discuss two central ideas in the philosophy of chemistry. These are the distinction between elements as simple substances (element-1) and elements as basic substances (element-2) and Paneth's proposed intermediate position for philosophy of chemistry. The response also discusses the question of isotopes in relationship to the nature of the elements and their classification (...) as well as the philosophical status of atomic orbitals. (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)

According to ontological reductionism, molecular chemistry refers, at last, to the quantum ontology; therefore, the ontological commitments of chemistry turn out to be finally grounded on quantum mechanics. The main problem of this position is that nobody really knows what quantum ontology is. The purpose of this work is to argue that the confidence in the existence of the physical entities described by quantum mechanics does not take into account the interpretative problems of the theory: in the discussions about the (...) relationship between chemistry and physics, difficulties are seen only on the side of chemistry, whereas matters highly controversial on the side of physics are taken for granted. For instance, it is usually supposed that the infinite mass limit in the Born-Oppenheimer approximation leads by itself to the concept of molecular framework used in molecular chemistry. We will argue that this assumption is implicitly based on an interpretative postulate for quantum mechanics, which, in turn, runs into difficulties when applied to the explanation of the simplest model of the hydrogen atom. (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)

The aim of the present paper is to analyze the problem of the relationship between chemistry and physics, by focusing on the widely discussed case of the atomic orbitals. We will begin by remembering the difference between the physical and the chemical interpretation of the concept of orbital. Then, we will refer to the claim made in 1999 that atomic orbitals have been directly imaged for the first time. On this basis, we will analyze the problem from a new approach, (...) by comparing the concept of orbital used in physics with the concept of orbital used in chemistry. Such an analysis will allow us to argue for an ontological pluralism that admits the coexistence of different ontologies without priorities or metaphysical privileges. From this philosophical framework, the concepts of chemical orbital and physical orbital correspond to two different ontologies. As a consequence, chemical orbitals are real entities belonging to the ontology of molecular chemistry, and can be observed like any other entity not belonging to the quantum mechanical ontology. DOI:10.5007/1808-1711.2010v14n3p309. (shrink)