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)

In the present paper we address the problem of optical isomerism embodied in the socalled “Hund’s paradox”, which points to the difficulty to account for chirality by means of quantum mechanics. In particular, we explain the answer to the problem proposed by the theory of decoherence. The purpose of this article is to challenge this answer on the basis of a conceptual analysis of the phenomenon of decoherence, that reveals the limitations of the theory of decoherence to solve the difficulties (...) posed by optical isomerism and, in general, by quantum measurement. (shrink)

One of the most plausible and widely discussed examples of strong emergence is molecular structure. The only detailed account of it, which has been very influential, is due to Robin Hendry and is formulated in terms of downward causation. This paper explains Hendry’s account of the strong emergence of molecular structure and argues that it is coherent only if one assumes a diachronic reflexive notion of downward causation. However, in the context of this notion of downward causation, the strong emergence (...) of molecular structure faces three challenges that have not been met and which have so far remained unnoticed. First, the putative empirical evidence presented for the strong emergence of molecular structure equally undermines supervenience, which is one of the main tenets of strong emergence. Secondly, it is ambiguous how the assumption of determinate nuclear positions is invoked for the support of strong emergence, as the role of this assumption in Hendry’s argument can be interpreted in more than one way. Lastly, there are understandings of causation which render the postulation of a downward causal relation between a molecule’s structure and its quantum mechanical entities, untenable. (shrink)

In a recent article entitled “The problem of molecular structure just is the measurement problem”, Alexander Franklin and Vanessa Seifert argue that insofar as the quantum measurement problem is solved, the problems of molecular structure are resolved as well. The purpose of the present article is to show that such a claim is too optimistic. Although the solution of the quantum measurement problem is relevant to how the problem of molecular structure is faced, such a solution is not sufficient to (...) account for the structure of molecules as understood in the field of chemistry. (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)

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)

Although during the last decades the philosophy of chemistry has greatly extended its thematic scope, the main difficulties appear in the attempt to link the chemical description of atoms and molecules and the description supplied by quantum mechanics. The aim of this paper is to analyze how the difficulties that threaten the continuous conceptual link between molecular chemistry and quantum mechanics can be overcome or, at least, moderated from the perspective of BM. With this purpose, in “The quantum-mechanical challenges” section (...) the foundational incompatibility between chemical and SQM descriptions will be briefly recalled. “Bohmian mechanics” section will be devoted to explain the main features of BM. In “Empirical equivalence and underdetermination” section, the consequences of the empirical equivalence between SQM and BM will be discussed. Finally, in the Conclusion, we will stress the scope of the obtained conclusions and the philosophical difficulties that still remain even after adopting BM for foundational purposes. (shrink)

John Earman's recent proposal that a substantive version of general covariance consists in the requirement that diffeomorphism invariance be a gauge symmetry is critically assessed. I argue that such a principle does not serve to differentiate general relativity from pre-relativistic theories. A model-theoretic characterization of two formulations of specially-relativistic theories is suggested. Diffeomorphisms are symmetries of only one such style of formulation and, I argue, Earman's proposal does not provide a reason to deny diffeomorphisms the status of gauge transformations relative (...) to this formulation. Carlo Rovelli's distinction between "passive" and "active" diffeomorphism invariance is also clarified. (shrink)

This is the first of two papers concerned with the philosophical significance of dualities as applied in recent fundamental physics. The general idea is that, for its peculiarity, this ‘new’ ingredient in theory construction can open unexpected perspectives in the current philosophical reflection on contemporary physics. In particular, today’s physical dualities represent an unusual type of intertheory relation, the meaning of which deserves to be investigated. The aim is to show how discussing this point brings into play, at the same (...) time, what is intended by a 'theory’ and in which sense dualities are to be considered 'symmetries'. This paper is introductory and focusses on the first form of duality explicitly applied in twentieth century physics, that is electromagnetic duality as discussed in Dirac’s theory of magnetic poles. The extension of electromagnetic duality in the context of quantum field theory and string theory is explored in a forthcoming companion paper. (shrink)

I will sketch a possible way of empirical/operational definition of space and time tags of physical events, without logical or operational circularities and with a minimal number of conventional elements. As it turns out, the task is not trivial; and the analysis of the problem leads to a few surprising conclusions.

Quantum mechanical entangled configurations of particles that do not satisfy Bell’s inequalities, or equivalently, do not have a joint probability distribution, are familiar in the foundational literature of quantum mechanics. Nonexistence of a joint probability measure for the correlations predicted by quantum mechanics is itself equivalent to the nonexistence of local hidden variables that account for the correlations (for a proof of this equivalence, see Suppes and Zanotti, 1981). From a philosophical standpoint it is natural to ask what sort of (...) concept can be used to provide a “joint” analysis of such quantum correlations. In other areas of application of probability, similar but different problems arise. A typical example is the introduction of upper and lower probabilities in the theory of belief. A person may feel uncomfortable assigning a precise probability to the occurrence of rain tomorrow, but feel comfortable saying the probability should be greater than ½ and less than ⅞. Rather extensive statistical developments have occurred for this framework. A thorough treatment can be found in Walley (1991) and an earlier measurement-oriented development in Suppes (1974). It is important to note that this focus on beliefs, or related Bayesian ideas, is not concerned, as we are here, with the nonexistence of joint probability distributions. Yet earlier work with no relation to quantum mechanics, but focused on conditions for existence has been published by many people. For some of our own work on this topic, see Suppes and Zanotti (1989). Still, this earlier work naturally suggested the question of whether or not upper and lower measures could be used in quantum mechanics, as a generalization of.. (shrink)

Norton has recently argued that causation is merely a useful folk concept and that it fails to hold for some simple systems even in the supposed paradigm case of a causal physical theory – namely Newtonian mechanics. The purpose of this article is to argue against this devaluation of causality in physics. My main argument is that Norton’s alleged counterexample to causality within standard Newtonian physics fails to obey what I shall call the causal core of Newtonian mechanics. In particular, (...) I argue, Norton’s example is not in conformity with Newton’s first law. Moreover, Norton’s reformulation of this first law seems insufficient as a replacement for the original version since the notion of inertial frames in the resulting reformulated theory lacks a physical justification, and since an intelligible notion of time in Newtonian mechanics appears to be closely tied to Newton’s first law in its standard form. I will finally suggest how, given a plausible relationist account of time, the causal core of Newtonian mechanics may play a central role also in relativity and quantum theory. (shrink)

During the 1930s and 1940s, American physical organic chemists employed electronic theories of reaction mechanisms to construct models offering explanations of organic reactions. But two molecular rearrangements presented enormous challenges to model construction. The Claisen and Cope rearrangements were predominantly inaccessible to experimental investigation and they confounded explanation in theoretical terms. Drawing on the idea that models can be autonomous agents in the production of scientific knowledge, I argue that one group of models in particular were functionally autonomous from the (...) Hughes–Ingold theory. Cope and Hardy’s models of the Claisen and Cope rearrangements were resources for the exploration of the Hughes–Ingold theory that otherwise lacked explanatory power. By generating ‘how-possibly’ explanations, these models explained how these rearrangements could happen rather than why they did happen. Furthermore, although these models were apparently closely connected to theory in terms of their construction, I argue that partial autonomy issued in extra-logical factors concerning the attitudes of American chemists to the Hughes–Ingold theory. And in the absence of a complete theoretical hegemony, a degree of consensus was reached concerning modelling the Claisen rearrangement mechanism.Keywords: Models; Explanation; Physical organic chemistry; Rearrangements. (shrink)

Harold Kincaid in Individualism and the Unity of Science postulates a model of unity-without-reduction in order to accurately describe the relation between individualism and macroeconomics. I present this model and apply it to the description of the relation between chemistry and quantum mechanics. I argue that, when it comes to the description of molecular structure, chemistry and quantum mechanics are unified in Kincaid’s sense. Specifically, the two disciplines contribute to the formation of a unified body of knowledge with respect to (...) molecular structure. (shrink)

The problems that exist in relating quantum mechanical phenomena to classical concepts like properties, causes, or entities like particles or waves are well-known and still open to question, so that there is not yet an agreement on what kind of metaphysics lies at the foundations of quantum mechanics. However, physicists constantly use the formal resources of quantum mechanics in order to explain quantum phenomena. The structural account of explanation, therefore, tries to account for this kind of mathematical explanation in physics, (...) and hinges on the following claims: i) scientific models are central in scientific explanation; ii) in some cases the relevant information for the explanation/understanding of a phenomenon P consists in the sole structural properties of the (models displayed by the) theory; iii) in these cases, the interpretation of the formalism in terms of a categorial framework is unessential for the explanation of P and a mathematical model can be at the base of an objective and effective scientific explanation. The present paper will carry a reflection about some issues arising from R.I.G. Hughes and Robert Clifton’s works in the attempt to outline some details of structural explanation. (shrink)

According to conventional wisdom, local gauge symmetry is not a symmetry of nature, but an artifact of how our theories represent nature. But a study of the so-called theta-vacuum appears to refute this view. The ground state of a quantized non-Abelian Yang-Mills gauge theory is characterized by a real-valued, dimensionless parameter theta—a fundamental new constant of nature. The structure of this vacuum state is often said to arise from a degeneracy of the vacuum of the corresponding classical theory, which degeneracy (...) allegedly arises from the fact that “large” (but not “small”) local gauge transformations connect physically distinct states of zero field energy. If that is right, then some local gauge transformations do generate empirical symmetries. In defending conventional wisdom against this challenge I hope to clarify the meaning of empirical symmetry while deepening our understanding of gauge transformations. I distinguish empirical from theoretical symmetries. Using Galileo’s ship and Faraday’s cube as illustrations, I say when an empirical symmetry is implied by a theoretical symmetry. I explain how the theta-vacuum arises, and how “large” gauge transformations differ from “small” ones. I then present two analogies from elementary quantum mechanics. By applying my analysis of the relation between empirical and theoretical symmetries, I show which analogy faithfully portrays the character of the vacuum state of a classical non-Abelian Yang-Mills gauge theory. The upshot is that “large” as well as “small” gauge transformations are purely formal symmetries of non-Abelian Yang-Mills gauge theories, whether classical or quantized. It is still worth distinguishing between these kinds of symmetries. An analysis of gauge within the constrained-Hamiltonian formalism yields the result that “large” gauge transformations should not be classified as gauge transformations; indeed, nor should “global” gauge transformations. In a theory in which boundary conditions are modeled dynamically, “global” gauge transformations may be associated with physical symmetries, corresponding to translations of these extra dynamical variables. Such translations are symmetries if and only if charge is conserved. But it is hard to argue that these symmetries are empirical, and in any case they do not correspond to any constant phase change in a quantum state. (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)

Although during the last decades the philosophy of chemistry has greatly extended its thematic scope, the main difficulties appear in the attempt to link the chemical description of atoms and molecules and the description supplied by quantum mechanics. The aim of this paper is to analyze how the difficulties that threaten the continuous conceptual link between molecular chemistry and quantum mechanics can be overcome or, at least, moderated from the perspective of BM. With this purpose, in “The quantum-mechanical challenges” section (...) the foundational incompatibility between chemical and SQM descriptions will be briefly recalled. “Bohmian mechanics” section will be devoted to explain the main features of BM. In “Empirical equivalence and underdetermination” section, the consequences of the empirical equivalence between SQM and BM will be discussed. Finally, in the Conclusion, we will stress the scope of the obtained conclusions and the philosophical difficulties that still remain even after adopting BM for foundational purposes. (shrink)

To explain phenomenon R by showing how mechanism M yields output R each time it is triggered by circumstances C, is to give a causal explanation of R. This paper analyses what mechanistic analysis can contribute to our understanding of causation in general and of downward causation in particular. It is first shown, against Glennan, that the concept of causation cannot be reduced to that of mechanism. Second it is shown, against Craver and Bechtel, that mechanistic explanation allows us to (...) make sense of causal processes that cut across levels, either in bottom-up direction where a change in a part of a system causes a change in the whole, or in downward direction where a change at the level of the system causes a change at the level of its parts. I suggest construing a decision's influence on molecules in muscle cells as a global constraint. Microscopic laws determine the detailed evolution of muscle cells and glucose molecules, but this evolution is constrained by the fact that it must be compatible with the action caused by the decision. (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)

When young Kant meditated upon the distinction between his right and left hands, he could not foresee that the problem of incongruent counterparts would revive in the twentieth century under a new form. In the early days of quantum chemistry, Friedrich Hund developed the so-called Hund paradox that arises from the supposed inability of quantum mechanics to account for the difference between enantiomers. In this paper, the paradox is expressed as a case of quantum measurement, stressing that decoherence does not (...) offer a way out of the problem. The main purpose is to argue for the need to adopt a clear interpretation of quantum mechanics in order to solve the paradox. In particular, I claim that the Modal-Hamiltonian Interpretation, which conceives measurement as a breaking-symmetry process, supplies the tools required to explain the dextro-rotation or levo-rotation properties of optical isomers. (shrink)

This volume collects papers presented at the Founding Conference of the European Philosophy of Science Association meeting, held November 2007. It provides an excellent overview of the state of the art in philosophy of science in different European countries.

INCONTINENCE, HONOURING SUNK COSTS AND RATIONALITY According to a basic principle of rationality, the decision to engage in a course of action should be determined solely by the analysis of its consequences. Thus, considerations associated with previous use of resources should have no bearing on an agent’s decision-making process. Frequently, however, agents persist carrying on an activity they themselves judge to be nonoptimal under the circumstances because they have already allocated resources to that activity. When this is the case, agents (...) are said to be honouring sunk costs. Honouring sunk costs is thus typically viewed as irrational economic behaviour. Two striking findings of the psychological literature on the sunk cost effect are that it is, in general, not lessened by having taken previously courses in economics, and that agents who did take such courses and that do honour sunk costs seem to be frequently aware of a cognitive dissonance in their behaviour. Davidson’s account of the possibility conditions of incontinent action renders continent action materially unfeasible. The very idea of incontinent action becomes thus a hollow one. I’ll present an alternative description of these possibility conditions that renders continent action materially feasible, and both, continent and incontinent action, cognitively plausible. In a nutshell, my proposal rests upon the drawing of an essential cognitive contrast between explicit processes of deliberative reasoning and lower level heuristic procedures. I conclude the paper arguing that my redescription of incontinent action accounts for the above mentioned cognitive dissonance effect better than the alternatives and that viewing at least an important subset of behaviours of honouring sunk costs as incontinent actions will enable us to consider them as peculiar manifestations of a more general and meaningful pattern in human behaviour. (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.