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.

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)

Currently, there are almost as many conceptions of emergence as authors who address the issue. Most literature on the matter focuses either on discussing, evaluating and comparing particular contributions or accounts of emergence, or on assessing a particular case study. Our aim in this paper is rather different. We here set out to introduce a distinction that has not been sufficiently taken into account in previous discussions on this topic: the distinction between inter-domain emergence—a relation between items belonging to different (...) ontic domains—and intra-domain emergence—a relation between items belonging to a same ontic domain. Our final purpose is not to assume and defend a definite stance on emergence, but to stress the relevance of such distinction when attempting to argue for or against emergence, in the first place. We will also address the connections between emergence so distinguished and more general philosophical perspectives, suggesting where would reductionists and pluralists stand with respect to intra- and inter-domain emergence. (shrink)

Currently, there are almost as many conceptions of emergence as authors who address the issue. Most literature on the matter focuses either on discussing, evaluating and comparing particular contributions or accounts of emergence, or on assessing a particular case study. Our aim in this paper is rather different. We here set out to introduce a distinction that has not been sufficiently taken into account in previous discussions on this topic: the distinction between inter-domain emergence—a relation between items belonging to different (...) ontic domains—and intra-domain emergence—a relation between items belonging to a same ontic domain. Our final purpose is not to assume and defend a definite stance on emergence, but to stress the relevance of such distinction when attempting to argue for or against emergence, in the first place. We will also address the connections between emergence so distinguished and more general philosophical perspectives, suggesting where would reductionists and pluralists stand with respect to intra- and inter-domain emergence. (shrink)

The modal-Hamiltonian interpretation belongs to the modal family of interpretations of quantum mechanics. By endowing the Hamiltonian with the role of selecting the subset of the definite-valued observables of the system, it accounts for ideal and non-ideal measurements, and also supplies a criterion to distinguish between reliable and non-reliable measurements in the non-ideal case. It can be reformulated in an explicitly invariant form, in terms of the Casimir operators of the Galilean group, and the compatibility of the MHI with the (...) theory of decoherence has been proved. Nevertheless, perhaps its main advantage in the eyes of a scientist is given by its several applications to well-known physical situations, leading to results compatible with experimental evidence. The purpose of this paper is to add a new application to the list: the case of optical isomerism, which is a central issue for the philosophy of physics and of chemistry since it points to the core of the problem of the relationship between physics and chemistry. Here it will be shown that the MHI supplies a direct and physically natural solution to the problem, a solution that does not require putting classical assumptions in “by hand.”. (shrink)

El propósito del presente trabajo consiste en abordar la pregunta por la ontología de la química cuántica. Para ello nos concentraremos en el concepto de enlace químico desde la perspectiva de los dos enfoques a través de los cuales la ecuación de Schrödinger se aplica a los sistemas químicos moleculares: la teoría del enlace de valencia (EV) y la teoría del orbital molecular (OM). Sobre la base de la presentación de ambos enfoques y su comparación, señalaremos que, a pesar de (...) su denominación tradicional, no pueden considerarse estrictamente como teorías científicas, sino que se ajustan mejor a la noción de modelo; en particular, son modelos que incorporan conceptos y leyes tanto del ámbito de la mecánica cuántica como del de la química estructural. Estas consideraciones nos permitirán argumentar que la química cuántica no posee un referente ontológico autónomo, sino que se trata de un ámbito científico cuya vigencia descansa sobre su éxito práctico en el cálculo y la predicción. Finalmente, indicaremos de qué modo los enfoques EV y OM del enlace químico abren una nueva perspectiva respecto de la noción misma de modelo en ciencias empíricas. (shrink)

The general question to be considered in this paper points to the nature of the world described by chemistry: what is macro-chemical ontology like? In particular, we want to identify the ontological categories that underlie chemical discourse and chemical practice. This is not an easy task, because modern Western metaphysics was strongly modeled by theoretical physics. For this reason, we attempt to answer our question by contrasting macro-chemical ontology with the mainstream ontology of physics and of traditional metaphysics. In particular, (...) we introduce the distinction between stuff-ontology, proper of chemistry, and individual-ontology, proper of physics. These two ontologies differ from each other in the basic categories of their own structures. On this basis, we characterize individual-ontology in such a way that the features of stuff-ontology will arise by contrast with it. (shrink)

The autonomy of chemistry and the legitimacy of the philosophy of chemistry are usually discussed in the context of the issue of reduction of chemistry to physics, and defended making use of the failure of reductionistic claims. Until quite recent times a rather widespread viewpoint was, however, that the failure of reductionistic claims concerns actually epistemological aspect of reduction only, but the ontological reduction of chemistry to physics cannot be denied. The new problems of the autonomy of chemistry in the (...) context of reductionism seem to be ontological and metaphysical. In the present paper it is argued that there is no need for some kind of metaphysical-ontological underpinning for rejection of the secondary positions of chemistry and philosophy of chemistry with respect to physics and philosophy of physics. The issue can be elucidated in terms of the philosophy of science accepting practical realism (also known by other names). (shrink)

Ilya Prigogine was not a systematic author: his ideas, covering a wide arch of areas, are dispersed in his many writings. In particular, his philosophical thought has to be reconstructed mainly on the basis of his works in collaboration with Isabelle Stengers: La Nouvelle Alliance ( 1979 ), Order out of Chaos ( 1984 ), and Entre le Temps et l’Éternité ( 1988 ). In this paper I undertake that reconstruction in order to argue that Prigogine’s position, when read in (...) the light of Putnam’s internalist realism, can be characterized as an ontological pluralism. The main aim of this work is to show the striking parallelism between the philosophical views of Prigogine and Stengers and those of Hilary Putnam in Reason , Truth and History ( 1981 ). This task will lead me to critically review Prigogine’s general scientific program: the attempt to establish the foundations of objective irreversibility. (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)

Perhaps the hottest topic in the philosophy of chemistry is that of the relationship between chemistry and physics. The problem finds one of its main manifestations in the debate about the nature of molecular structure, given by the spatial arrangement of the nuclei in a molecule. The traditional strategy to address the problem is to consider chemical cases that challenge the definition of molecular structure in quantum–mechanical terms. Instead of taking that top-down strategy, in this paper we face the problem (...) of the reduction of molecular structure to quantum mechanics from a bottom-up perspective: our aim is to show how the theoretical peculiarities of quantum mechanics stand against the possibility of molecular structure, defined in terms of the spatial relations of the nuclei conceived as individual localized objects. We will argue that, according to the theory, quantum “particles” are not individuals that can be identified as different from others and that can be reidentified through time; therefore, they do not have the ontological stability necessary to maintain the relations that can lead to a spatially definite system with an identifiable shape. On the other hand, although quantum chemists use the resources supplied by quantum mechanics with successful results, this does no mean reduction: their “approximations” add certain assumptions that are not justified in the context of quantum mechanics or are even inconsistent with the very formal structure of the theory. (shrink)

The past decade or so has witnessed an increase in the number of philosophical discussions about emergence and reduction in science. However, many of these discussions (though not all) remain too abstract and theoretical, and are wanting with respect to concrete examples taken from the sciences. This dissertation studies the topics of reduction and emergence in the context of a case study. I focus on the case of chemistry and investigate how emergentism can help us secure the autonomy of this (...) discipline in relation to the underlying microphysics. I develop an account of emergence (called functional emergence) that is, I argue, capable of answering the question of why we have chemistry instead of just applied quantum mechanics. I argue that functionally emergent properties in chemistry -- properties that are defined by their behaviour, not by some shared microphysical constituent -- can help us defend the autonomy of chemistry; they allow for the existence of sui generis chemical regularities, which can be used in sui generis chemical explanations. Functional emergence generates difficulties for some accounts of inter-theoretic reduction, but unlike other theories of emergence it is compatible with weaker forms of reductionism. (shrink)

The many-faced relationship between chemistry and physics is one of the most discussed topics in the philosophy of chemistry. In his recent book Reducing Chemistry to Physics. Limits, Models, Consequences, Hinne Hettema conceives this relationship as a reduction link, and devotes his work to defend this position on the basis of a “naturalized” concept of reduction. In the present paper I critically review three kinds of issues stemming from Hettema’s argumentation: philosophical, scientific and methodological.

This paper discusses the proposal made by Lombardi and Labarca (Found Chem 7:125–148, 2005) that internal realism can secure the ontological autonomy of chemistry. I argue that internal realism is not, by itself, sufficient to accomplish this task. The fact that conceptual schemes may differ with respect to their theoretical virtues, and the possibility that the relations between them may be reductive undermine the premise that each conceptual scheme has an equal right to define its own ontology, which is a (...) key premise in Lombardi and Labarca’s proposal. (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)

The analysis of the concept of orbital allows us to argue that—in opposition to a recent position in philosophy of science—it is impossible to defend the autonomy of the chemical reality in regard to physical reality, appealing to the idea that there is a conceptual rupture among a chemical interpretation and a quantuminterpretation of the concept. This is the case because there are not two different interpretations of the concept of orbital. On the contrary, the concept involved in structural chemistry (...) and in quantum chemistry comes from quantum mechanics.El análisis del concepto de orbital permite argumentar—en oposición a una propuesta reciente en filosofía de la química—que no es posible defender la autonomía ontológica de la realidad química respecto de la física, sobre la base de una ruptura conceptual entre una interpretación química del concepto y otra propia de la mecánica cuántica. Esto es así porque no existen tales interpretaciones distintas del concepto de orbital, sino que, por el contrario, este concepto en química cuántica y en química estructural proviene de la mecánica cuántica. (shrink)