Statistical mechanics is one of the crucial fundamental theories of physics, and in his new book Lawrence Sklar, one of the pre-eminent philosophers of physics, offers a comprehensive, non-technical introduction to that theory and to attempts to understand its foundational elements. Among the topics treated in detail are: probability and statistical explanation, the basic issues in both equilibrium and non-equilibrium statistical mechanics, the role of cosmology, the reduction of thermodynamics to statistical mechanics, and the alleged foundation of the very notion (...) of time asymmetry in the entropic asymmetry of systems in time. The book emphasises the interaction of scientific and philosophical modes of reasoning, and in this way will interest all philosophers of science as well as those in physics and chemistry concerned with philosophical questions. The book could also be read by an informed general reader interested in the foundations of modern science. (shrink)

This is a companion to another paper. Together they rebut two widespread philosophical doctrines about emergence. The first, and main, doctrine is that emergence is incompatible with reduction. The second is that emergence is supervenience; or more exactly, supervenience without reduction.In the other paper, I develop these rebuttals in general terms, emphasising the second rebuttal. Here I discuss the situation in physics, emphasising the first rebuttal. I focus on limiting relations between theories and illustrate my claims with four examples, each (...) of them a model or a framework for modelling, from well-established mathematics or physics.I take emergence as behaviour that is novel and robust relative to some comparison class. I take reduction as, essentially, deduction. The main idea of my first rebuttal will be to perform the deduction after taking a limit of some parameter. Thus my first main claim will be that in my four examples (and many others), we can deduce a novel and robust behaviour, by taking the limit N→∞ of a parameter N.But on the other hand, this does not show that the N=∞ limit is “physically real”, as some authors have alleged. For my second main claim is that in these same examples, there is a weaker, yet still vivid, novel and robust behaviour that occurs before we get to the limit, i.e. for finite N. And it is this weaker behaviour which is physically real.My examples are: the method of arbitrary functions (in probability theory); fractals (in geometry); superselection for infinite systems (in quantum theory); and phase transitions for infinite systems (in statistical mechanics). (shrink)

This paper analyses Richard Bader’s ‘operational’ view of quantum mechanics and the role it plays in the the explanation of chemistry. I argue that QTAIM can partially be reconstructed as an ‘austere’ form of quantum mechanics, which is in turn committed to an eliminative concept of reduction that stems from Kemeny and Oppenheim. As a reductive theory in this sense, the theory fails. I conclude that QTAIM has both a regulatory and constructive function in the theories of chemistry.

Chemistry and physics are two sciences that are hard to connect. Yet there is significant overlap in their aims, methods, and theoretical approaches. In this book, the reduction of chemistry to physics is defended from the viewpoint of a naturalised Nagelian reduction, which is based on a close reading of Nagel's original text. This naturalised notion of reduction is capable of characterising the inter-theory relationships between theories of chemistry and theories of physics. The reconsideration of reduction also leads to a (...) new characterisation of chemical theories. This book is primarily aimed at philosophers of chemistry and chemists with an interest in philosophy, but is also of interest to the general philosopher of science. (shrink)

The quantum theory of atoms in molecules (QTAIM) uses physics to define an atom and its contribution to observable properties in a given system. It does so using the electron density and its flow in a magnetic field, the current density. These are the two fields that Schrödinger said should be used to explain and understand the properties of matter. It is the purpose of this paper to show how QTAIM bridges the conceptual gulf that separates the observations of chemistry (...) from the realm of physics and do so in a manner that is both rigorous and conceptually simple. Since QTAIM employs real measurable fields, it enables one to present the findings of complex quantum mechanical calculations in a pictorial manner that isolates the essential physics. The time has arrived for a sea change in our attempts to predict and classify the observations of chemistry, time to replace the use of simplified and arbitrary models with the full predictive power of physics, as applied to an atom in a molecule. (shrink)

This treatise presents thoughts on the divide that exists in chemistry between those who seek their understanding within a universe wherein the laws of physics apply and those who prefer alternative universes wherein the laws are suspended or ‘bent’ to suit preconceived ideas. The former approach is embodied in the quantum theory of atoms in molecules (QTAIM), a theory based upon the properties of a system’s observable distribution of charge. Science is experimental observation followed by appeal to theory that, upon (...) occasion, leads to new experiments. This is the path that led to the development of the molecular structure hypothesis—that a molecule is a collection atoms with characteristic properties linked by a network of bonds that impart a structure—a concept forged in the crucible of nineteenth century experimental chemistry. One hundred and fifty years of experimental chemistry underlie the realization that the properties of some total system are the sum of its atomic contributions. The concept of a functional group, consisting of a single atom or a linked set of atoms, with characteristic additive properties forms the cornerstone of chemical thinking of both molecules and crystals and Dalton’s atomic hypothesis has emerged as the operational theory of chemistry. We recognize the presence of a functional group in a given system and predict its effect upon the static, reactive and spectroscopic properties of the system in terms of the characteristic properties assigned to that group. QTAM gives physical substance to the concept of a functional group. (shrink)

Emergence is a notorious philosophical term of art. A variety of theorists have appropriated it for their purposes ever since George Henry Lewes gave it a philosophical sense in his 1875 Problems of Life and Mind. We might roughly characterize the shared meaning thus: emergent entities (properties or substances) ‘arise’ out of more fundamental entities and yet are ‘novel’ or ‘irreducible’ with respect to them. (For example, it is sometimes said that consciousness is an emergent property of the brain.) Each (...) of the quoted terms is slippery in its own right, and their specifications yield the varied notions of emergence that we discuss below. There has been renewed interest in emergence within discussions of the behavior of complex systems and debates over the reconcilability of mental causation, intentionality, or consciousness with physicalism. (shrink)

This is one of two papers about emergence, reduction and supervenience. It expounds these notions and analyses the general relations between them. The companion paper analyses the situation in physics, especially limiting relations between physical theories. I shall take emergence as behaviour that is novel and robust relative to some comparison class. I shall take reduction as deduction using appropriate auxiliary definitions. And I shall take supervenience as a weakening of reduction, viz. to allow infinitely long definitions. The overall claim (...) of this paper will be that emergence is logically independent both of reduction and of supervenience. In particular, one can have emergence with reduction, as well as without it; and emergence without supervenience, as well as with it. Of the subsidiary claims, the four main ones are: : I defend the traditional Nagelian conception of reduction ; : I deny that the multiple realizability argument causes trouble for reductions, or ``reductionism'' ; : I stress the collapse of supervenience into deduction via Beth's theorem ; : I adapt some examples already in the literature to show supervenience without emergence and vice versa. (shrink)

I discuss here a number of different kinds of diachronic emergence, noting that they differ in important ways from synchronic conceptions. I argue that Bedau’s weak emergence has an essentially historical aspect, in that there can be two indistinguishable states, one of which is weakly emergent, the other of which is not. As a consequence, weak emergence is about tokens, not types, of states. I conclude by examining the question of whether the concept of weak emergence is too weak and (...) note that there is at present no unifying account of diachronic and synchronic concepts of emergence. (shrink)

This paper analyzes the generation and function of hitherto ignored or misrepresented interfield theories , theories which bridge two fields of science. Interfield theories are likely to be generated when two fields share an interest in explaining different aspects of the same phenomenon and when background knowledge already exists relating the two fields. The interfield theory functions to provide a solution to a characteristic type of theoretical problem: how are the relations between fields to be explained? In solving this problem (...) the interfield theory may provide answers to questions which arise in one field but cannot be answered within it alone, may focus attention on domain items not previously considered important, and may predict new domain items for one or both fields. Implications of this analysis for the problems of reduction and the unity and progress of science are mentioned. (shrink)

This paper explicates two notions of emergencewhich are based on two ways of distinguishinglevels of properties for dynamical systems.Once the levels are defined, the strategies ofcharacterizing the relation of higher level to lower levelproperties as diachronic and synchronic emergenceare the same. In each case, the higher level properties aresaid to be emergent if they are novel or irreducible with respect to the lower level properties. Novelty andirreducibility are given precise meanings in terms of the effectsthat the change of a bifurcation (...) or perturbation parameterin the system has. (The same strategy can be applied to otherways of separating levels of properties, like themicro/macro distinction.)The notions of emergence developed here are notions of emergencein a weak sense: the higher level emergent properties wecapture are always structural properties (or are realized insuch properties), that is, they are defined in terms of the lowerlevel properties and their relations. Diachronic and synchronicemergent properties are distinctions within thecategory of structural properties. (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)

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 main thrust of the paper involves a theoretical and philosophical analysis of the claim made in September 1999 that atomic orbitals have been directly imaged for the first time. After a brief account of the recent claims the paper reviews the development of the orbit and later orbital concepts and analyzes the theoretical status of atomic orbitals. The conclusion is that contrary to these claims, atomic orbitals have not in fact been observed. The non-referring nature of modern atomic orbitals (...) is discussed in the context of Laudan's writings on realism, the success of theories, and whether or not scientific terms refer. I conclude that the failure to observe orbitals is a good prima facie case for divorcing the success of theories from the question of whether their central terms refer. The added relevance of this case is that it concerns a current and highly successful theory. Finally, the relevance of this ‘floating model’ to contemporary discussions on scientific models is briefly considered. (shrink)

We reconsider the Nagelian theory of reduction and argue that, contrary to a widely held view, it is the right analysis of intertheoretic reduction. The alleged difficulties of the theory either vanish upon closer inspection or turn out to be substantive philosophical questions rather than knock-down arguments.

This paper attempts a critical reappraisal of Nagel's (1961, 1970) model of reduction taking into account both traditional criticisms and recent defenses. This model treats reduction as a type of explanation in which a reduced theory is explained by a reducing theory after their relevant representational items have been suitably connected. In accordance with the deductive-nomological model, the explanation is supposed to consist of a logical deduction. Nagel was a pluralist about both the logical form of the connections between the (...) reduced and reducing theories (which could be conditionals or biconditionals) and their epistemological status (as analytic connections, conventions, or synthetic claims). This paper defends Nagel's pluralism on both counts and, in the process, argues that the multiple realizability objection to reductionism is misplaced. It also argues that the Nagel model correctly characterizes reduction as a type of explanation. However, it notes that logical deduction must be replaced by a broader class of inferential techniques that allow for different types of approximation. Whereas Nagel (1970), in contrast to his earlier position (1961), recognized the relevance of approximation, he did not realize its full import for the model. Throughout the paper two case studies are used to illustrate the arguments: the putative reduction of classical thermodynamics to the kinetic theory of matter and that of classical genetics to molecular biology. (shrink)

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.

A variety of recent philosophical discussions, particularly on topics relating to complexity, have begun to reemploy the concept of 'emergence'. Although multiple concepts of 'emergence' are available, little effort has been made to systematically distinguish them. In this paper, I provide a taxonomy of higher-order properties that (inter alia) distinguishes three classes of emergent properties: (1) ontologically basic properties of complex entities, such as the mythical vital properties, (2) fully configurational properties, such as mental properties as they are conceived of (...) by functionalists and computationalists, and (3) highly configurational/holistic properties, such as the higher-level patterns characteristic of complex dynamical systems. Or more simply: emergence as ontological liberality, emergence as multiple realizability, and emergence as interactive complexity. (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)

In this paper I briefly reply to Shant Shahbazian’s comments on my paper “Austere quantum mechanics as a reductive basis for chemistry” and argue that quantum theory of atoms in molecules can be characterised as a research programme in the theories of chemistry. I also explore the areas in which Shahbazian and me agree and disagree.

In this paper, I propose two theses, and then examine what the consequences of those theses are for discussions of reduction and emergence. The first thesis is that what have traditionally been seen as robust, reductions of one theory or one branch of science by another more fundamental one are a largely a myth. Although there are such reductions in the physical sciences, they are quite rare, and depend on special requirements. In the biological sciences, these prima facie sweeping reductions (...) fade away, like the body of the famous Cheshire cat, leaving only a smile.... The second thesis is that the "smiles" are fragmentary patchy explanations, and though patchy and fragmentary, they are very important, potentially Nobel-prize winning advances. To get the best grasp of these "smiles," I want to argue that, we need to return to the roots of discussions and analyses of scientific explanation more generally, and not focus mainly on reduction models, though three conditions based on earlier reduction models are retained in the present analysis. I briefly review the scientific explanation literature as it relates to reduction, and then offer my account of explanation. The account of scientific explanation I present is one I have discussed before, but in this paper I try to simplify it, and characterize it as involving field elements and a preferred causal model system abbreviated as FE and PCMS. In an important sense, this FE and PCMS analysis locates an "explanation" in a typical scientific research article. This FE and PCMS account is illustrated using a recent set of neurogenetic papers on two kinds of worm foraging behaviors: solitary and social feeding. One of the preferred model systems from a 2002 Nature article in this set is used to exemplify the FE and PCMS analysis, which is shown to have both reductive and nonreductive aspects. The paper closes with a brief discussion of how this FE and PCMS approach differs from and is congruent with Bickle's "ruthless reductionism" and the recently revived mechanistic philosophy of science of Machamer, Darden, and Craver. (shrink)

In this paper I discuss some consequences and manifestations of a mereology of structured wholes in chemistry, with particular reference to the concept of atoms in molecules.

To be, or not to be, that is the question…In his wonderful Facts and Mysteries, Martinus Veltman terminates a section with an anecdote: “When quarks were not immediately discovered after the introduction by Gell-Mann he took to calling them symbolic, saying they were indices. In the early seventies I met him at CERN and he again said something in that spirit. I then jumped up, coming down with some impact that made the floor tremble, and asked him: Do I look (...) like a heap of indices? This visibly rattled him, and indeed after that he no more advocated this vision, at least not as far as I know” (see page 240 in Veltman 2003). Although it is probable that Murray Gell-Mann, the inventor of quarks, has changed his mind regarding the reality of his symbols after this tough conversation, even later in the start of eighties the reality of quarks, as basic constituents of protons and neutrons, was a matter of disputes and exchanges (Shrader-Frechette 1982a, b; Albright 1982; Gruender 1982). A g. (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 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)

Recently, the author of this paper and his research team have extended the orthodox quantum theory of atoms in molecules (QTAIM) to a novel paradigm called the two-component QTAIM (TC-QTAIM). This extended framework enables one to incorporate nuclear dynamics into the AIM analysis as well as performing AIM analysis of the exotic species; positronic and muonic species are a few examples. In present paper, this framework has been reviewed, providing some computational examples with particular emphasis on origins and applications, in (...) a non-technical language. The main questions, enigmas and basic ideas that finally yielded the TC-QTAIM are considered in chronological order to help the reader comprehend the intuition behind the math. Finally, it is demonstrated that the TC-QTAIM and its more refined versions are able to tackle problems inaccessible to the orthodox QTAIM. (shrink)

The article disputes the recent claim featured in "Nature" magazine and many other science magazines to the effect that atomic orbitals have been observed for the first time. The claim is incorrect in view of the unconvincing nature of the evidence adduced and since atomic orbitals are deemed unobservable in principle by quantum mechanics. In addition, the possible educational drawbacks of this incorrect claim are discussed.

In this paper I investigate two views of theoretical explanation in quantum chemistry, advocated by John Clarke Slater and Charles Coulson. Slater argued for quantum‐mechanical rigor, and the primacy of fundamental principles in models of chemical bonding. Coulson emphasized systematic explanatory power within chemistry, and continuity with existing chemical explanations. I relate these views to the epistemic contexts of their disciplines.

The interpretation of the concept of reduced state is a subtle issue that has relevant consequences when the task is the interpretation of quantum mechanics itself. The aim of this paper is to argue that reduced states are not the quantum states of subsystems in the same sense as quantum states are states of the whole composite system. After clearly stating the problem, our argument is developed in three stages. First, we consider the phenomenon of environment-induced decoherence as an example (...) of the case in which the subsystems interact with each other; we show that decoherence does not solve the measurement problem precisely because the reduced state of the measuring apparatus is not its quantum state. Second, the non-interacting case is illustrated in the context of no-collapse interpretations, in which we show that certain well-known experimental results cannot be accounted for due to the fact that the reduced states of the measured system and the measuring apparatus are conceived as their quantum states. Finally, we prove that reduced states are a kind of coarse-grained states, and for this reason they cancel the correlations of the subsystem with other subsystems with which it interacts or is entangled. (shrink)

Interpretation of experiments involving use of vacuum ultraviolet radiation to effect ionization of N 2 in terms of measurements of a molecular orbital is erroneous.

This paper first queries what type of concept of emergence, if any, could be connected with the different chemical activities subsumed under the label ‘quantum chemistry’. In line with Roald Hoffmann, we propose a ‘rotation to research laboratory’ in order to point out how practitioners hold a molecular whole, its parts, and the surroundings together within their various methods when exploring chemical transformation. We then identify some requisite contents that a concept of emergence must incorporate in order to be coherent (...) from the standpoint of the scientific practices involved. In this respect, we finally propose a relational form of emergence which pays attention to the constitutive role of the modes of intervention and to the co-definition of the levels of organization. No metaphysical distinction between the higher and basic levels of organization is supposed, but only a plurality of modes of access. Moreover, these modes of access are not construed as mere ways of revealing intrinsic patterns of organization but, on the contrary, are considered to be active elements on which the constitution of those patterns depends. What is at stake in this paper is therefore not an ontological form of emergence but an agnostic one which fits what chemists do in their daily work. (shrink)

The main thrust of the paper involves a theoretical and philosophical analysis of the claim made in September 1999 that atomic orbitals have been directly imaged for the first time. After a brief account of the recent claims the paper reviews the development of the orbit and later orbital concepts and analyzes the theoretical status of atomic orbitals. The conclusion is that contrary to these claims, atomic orbitals have not in fact been observed. The non-referring nature of modern atomic orbitals (...) is discussed in the context of Laudan's writings on realism, the success of theories, and whether or not scientific terms refer. I conclude that the failure to observe orbitals is a good prima facie case for divorcing the success of theories from the question of whether their central terms refer. The added relevance of this case is that it concerns a current and highly successful theory. Finally, the relevance of this 'floating model' to contemporary discussions on scientific models is briefly considered. (shrink)