Philosophical Perspectives in Quantum Chemistry (Synthese Library, 461) PDF
Preview Philosophical Perspectives in Quantum Chemistry (Synthese Library, 461)
Synthese Library 461 Studies in Epistemology, Logic, Methodology, and Philosophy of Science Olimpia Lombardi Juan Camilo Martínez González Sebastian Fortin Editors Philosophical Perspectives in Quantum Chemistry Synthese Library Studies in Epistemology, Logic, Methodology, and Philosophy of Science Volume 461 Editor-in-Chief OtávioBueno,DepartmentofPhilosophy,UniversityofMiami,CoralGables,USA EditorialBoardMembers BeritBrogaard,UniversityofMiami,CoralGables,USA AnjanChakravartty,DepartmentofPhilosophy,UniversityofMiami,CoralGables, USA StevenFrench,UniversityofLeeds,Leeds,UK CatarinaDutilhNovaes,VUAmsterdam,Amsterdam,TheNetherlands DarrellP.Rowbottom,DepartmentofPhilosophy,LingnanUniversity,TuenMun, HongKong Emma Ruttkamp, Department of Philosophy, University of South Africa, Pretoria, SouthAfrica Kristie Miller, Department of Philosophy, Centre for Time, University of Sydney, Sydney,Australia The aim of Synthese Library isto provide aforum for thebest currentwork inthe methodology and philosophy of science and in epistemology, all broadly under- stood.Awidevarietyofdifferentapproacheshavetraditionallybeenrepresentedin theLibrary,andeveryeffortismadetomaintainthisvariety,notforitsownsake,but because we believe that there are many fruitful and illuminating approaches to the philosophyofscienceandrelateddisciplines. Specialattentionispaidtomethodologicalstudieswhichillustratetheinterplayof empirical and philosophical viewpoints and to contributions to the formal (logical, set-theoretical, mathematical, information-theoretical, decision-theoretical, etc.) methodology of empirical sciences. Likewise, the applications of logical methods toepistemologyaswellasphilosophicallyandmethodologicallyrelevantstudiesin logicarestronglyencouraged.Theemphasisonlogicwillbetemperedbyinterestin the psychological, historical, and sociological aspects of science. In addition to monographsSyntheseLibrarypublishesthematicallyunifiedanthologiesandedited volumes with a well-defined topical focus inside the aim and scope of the book series.Thecontributionsinthevolumesareexpectedtobefocusedandstructurally organizedinaccordancewiththecentraltheme(s),andshouldbetiedtogetherbyan extensiveeditorialintroductionorsetofintroductionsifthevolumeisdividedinto parts.Anextensivebibliographyandindexaremandatory. Olimpia Lombardi Juan Camilo Martínez González Sebastian Fortin Editors Philosophical Perspectives in Quantum Chemistry Editors OlimpiaLombardi JuanCamiloMartínezGonzález UniversityofBuenosAiresandCONICET UniversityofBuenosAiresandCONICET CiudaddeBuenosAires,Argentina CiudaddeBuenosAires,Argentina SebastianFortin CONICET,UniversidaddeBuenosAires BuenosAires,Argentina ISSN0166-6991 ISSN2542-8292 (electronic) SyntheseLibrary ISBN978-3-030-98372-7 ISBN978-3-030-98373-4 (eBook) https://doi.org/10.1007/978-3-030-98373-4 ©SpringerNatureSwitzerlandAG2022 Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpartofthe materialisconcerned,specificallytherightsoftranslation,reprinting,reuseofillustrations,recitation, broadcasting,reproductiononmicrofilmsorinanyotherphysicalway,andtransmissionorinformation storageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilarmethodology nowknownorhereafterdeveloped. Theuseofgeneraldescriptivenames,registerednames,trademarks,servicemarks,etc.inthispublication doesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfromtherelevant protectivelawsandregulationsandthereforefreeforgeneraluse. The publisher, the authors and the editors are safe to assume that the advice and information in this bookarebelievedtobetrueandaccurateatthedateofpublication.Neitherthepublishernortheauthorsor theeditorsgiveawarranty,expressedorimplied,withrespecttothematerialcontainedhereinorforany errorsoromissionsthatmayhavebeenmade.Thepublisherremainsneutralwithregardtojurisdictional claimsinpublishedmapsandinstitutionalaffiliations. ThisSpringerimprintispublishedbytheregisteredcompanySpringerNatureSwitzerlandAG Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Working in philosophy of science is not easy when one lives in the southernmost country of South America. Furthermore, the community of the philosophy and foundations of chemistry is relatively small, and its members are scattered all over the world. Fortunately, current technology has facilitated communication and has madepossiblecertainprojectsthatwouldhavebeenunthinkableinpasttimes.This volumeisoneofthoseprojects. Thisvolumewasproducedduringveryhardtimes:thepandemichasturnedour livesupsidedowninmanyways,andwehavehadtoadapttoasituationthatwillbe remembered for a long time. In spite of this, today we are proud to present this volume about the philosophy of quantum chemistry, which would not have been possible without the effort and the commitment of all the authors who contributed withtheirworkstothisproject.Ourspecialrecognitiongoestoallofthem. Wewouldalsoliketorecallthesupportofthegroupofphilosophyofchemistry led by Olimpia, which, although based in Buenos Aires, includes researchers and students from other cities of Argentina: in addition to two of us, Juan Camilo Martínez González and Sebastian Fortin, also Hernán Accorinti, Fiorela Alassia, Jesús Jaimes Arriaga, and Alfio Zambon. Last, but not least, we would like to express our gratitude to Springer, in particular to the Synthese Library Series in the person of its editor-in-chief, Otávio Bueno, for his kind invitation to edit this volumeinthecontextoftheseries,andtoitsProjectCoordinator,PalaniMurgesani, forhispatienceandassistanceduringallthestagesofthisproject. CiudaddeBuenosAires,Argentina OlimpiaLombardi February2022 JuanCamiloMartínezGonzález SebastianFortin v Introduction At present, the philosophy of chemistry is a vigorous branch of the philosophy of science, congregating researchers from all around the world. The International SocietyforthePhilosophyofChemistry(ISPC),foundedin1997,sponsorsannual meetings since its foundation, in which scholars share their research results and discusscurrenttopicsofthearea.Thesubdisciplineisalsocoveredbytwospecial- ized publications, Foundations of Chemistry (since 1999, official journal of the ISPC), and Hyle–International Journal for Philosophy of Chemistry (since 1995). Despite this intense activity, the philosophy of chemistry has consolidated very recently when compared, for instance, with the philosophy of physics and the philosophy of biology, a fact that contrasts with the long history of chemistry as a scientific discipline. The question is what explains this relatively delayed consolidation. Although chemistry developed independently from physics until the end of the nineteenth century, its independence began to be questioned since the advent of quantum mechanics. The astonishing success of the quantum explanations supportedthebeliefinthepossibilityofaccountingfor allchemicalphenomenain physicalterms.Therefore,despitethescientificandmethodologicalpeculiaritiesof the chemical sciences, the assumption of the reduction of chemistry to quantum mechanics turned out to be a leitmotiv both in science and in philosophy. As a consequence,duringmostpartofthetwentiethcentury,itwasalsoassumedthatthe philosophical problems of chemistry were, when properly analyzed, problems for thephilosophyofphysics. In the face of this situation, it is not surprising that, when the philosophy of chemistry was introduced in the philosophical thinking in the last decades of the twentiethcentury,theproblemoftherelations betweenchemistry andphysicswas oneofthehottesttopics.Severalauthors,comingfrombothphilosophyandchem- istry,emphasizedtheneedtoadoptamorecarefulperspectivetocounteruncritical assumptionsofreduction.Infact,manycasestudiesforphilosophicalreflectionhave focused on concepts that inhabit the space between chemistry and physics. For instance, Lewis’s theory of chemical bond, conceived as a pair of electrons shared vii viii Introduction between atoms, was revised when approached from quantum physics: since elec- trons are elemental quantum particles, they are indistinguishable in principle and, consequently, cannot be identified in the constitution of a chemical bond. Another centralconceptthatneededtobereconsideredinthelightofquantummechanicswas molecular structure: whereas central for chemistry, the very notion of molecular structure finds no comfortable place in the quantum context because quantum particles cannot be conceived at rest in definite positions due to the Heisenberg Principle;furthermore,theveryexistenceofisomersseemstobechallengedbythe factthatquantumHamiltoniansdonotdistinguishbetweenthem.Butnotonlythis kindofconceptsisrevisitedasquantummechanicsenteredthestage;eventhenature oftheperiodictable,atheoretical constructthat liesattheveryheartofchemistry, hasbeentheobjectofreneweddiscussions.Someauthorsbelievethatthetableisin principle derivable from quantum physics, whereas others consider that chemical elements,withtheirpeculiarmacroscopicproperties,cannotbereducedbutemerge fromanunderlyingquantumdomain. Althoughthesequestionsaboutthelinksbetweenchemistryandphysicsalready constitute an important issue from a general viewpoint, they acquire a special relevance in the particular context of quantum chemistry, a field which, from its veryorigins,filledaproblematicpositioninthedisciplinaryspace.Ontheonehand, quantum chemistry is a subdiscipline of chemistry, in particular, a branch of theoretical chemistry. On the other hand, it appeals essentially to theoretical tools coming from physics to obtain its results. This intermediate position, while raising questions about its disciplinary identity, makes quantum chemistry a privileged arena for discussing inter-theoretic and inter-disciplinary relationships. One of the main approaches in quantum chemistry is the Density Functional Theory (DFT), whose purpose is to compute the properties of many-electron systems – typically molecules–bymeansoffunctionalsofthespatiallydependentelectronicdensity.In this context, the Hohenberg-Kohn (HK) theorems play a central role: the first HK theorem proves that the properties of a molecule in its ground state are uniquely determined by the electron density; the second HK theorem proves that an energy functional can be defined such that it is minimized by the ground-state electron density.Theotherapproachisthequantumtheoryofatomsinmolecules(QTAIM), whichaimsatdefiningchemicalbondingexclusivelyintermsofthetopologyofthe electronicdensity:byidentifyingtopologicalatoms,obtainedbydividingspaceinto volumescontainingonenucleusthatactsasanattractoroftheelectrondensity,the theory offers a quantum mechanical view of the structure of molecules. Both theoretical approaches, which combine an intensive use of quantum tools with molecular chemistry knowledge, open up a new perspective for the analysis of the manyandsubtlelinksbetweenchemistryandphysics. In addition to the theoretical dimension, quantum chemistry leads us to rethink ourphilosophicalpictureofscience,stronglyshapedontheimageofphysics.Infact, from the outset, quantum chemistry begins to outline its identity, not around a theoreticalbody,butasanactivitythatintegratestheoreticalelementsandmethod- ologicalstrategiescomingfromchemistry,physics,mathematics,andinformatics.In thiscontext,theappealtomodelsisnotonlypervasive,asinothersciences,butis Introduction ix also constitutive of the area as a scientific discipline. However, far from any representationalist purpose, quantum-chemical models play an essentially pragmatic role: they are used not only to predict chemical properties, but also to designnewsubstances.Itisalsointhissensethattheidentityofquantumchemistry isnotcommittedtoanyparticularontologicalreference,butratherreliesonabody ofpracticessharedbyascientificcommunityofresearchersfromawidevarietyof backgrounds. Itisinthisbroadcontextofnewtheoretical,historical,andmethodologicalissues that the question about the nature of quantum chemistry deserves to be considered from a conceptual viewpoint. The aim of this volume is, precisely, to address the subjectmatter from diverseperspectives, whichilluminate its different aspectsand implications. With this purpose, the articles of the volume are organized into three parts. PartI,“QuantumChemistry:HistoryandPractices,”groupsfourchaptersmainly devotedtoinquiringintotheverynatureofquantumchemistryfromhistoricaland pragmatic viewpoints. This part opens with the chapter “Quantum Chemistry in Historical Perspective,” in which Stylianos Kampouridis, Ana Simões, and Theodore Arabatzis provide a detailed and informed historical account of how quantumchemistrywasdevelopedbycrossingdisciplinaryfrontiersandintegrating newinstruments.Bydiscussingconceptual,institutional,methodological,andepis- temological matters, the authors show the path followed by quantum chemistry in the development of its identity as an in-between/boundary discipline. The second chapter, “How Chemical Is Quantum Chemistry?,” by Klaus Ruthenberg, also adopts a historical perspective, but in this case to draw attention to the deep breakdown between quantum chemistry and the macroscopic chemistry of sub- stances. The main purpose of the author is to point to the danger of overlooking thelimitationsofquantumchemistryinexplainingthebehaviorofsubstances,which needmacro-chemicalpracticesforeigntoquantummechanics.Inthethirdchapter, “Interacting Practices: Quantum Chemistry and Organic Synthesis,” William Goodwin characterizes quantum chemistry as an interfield theory and focuses on its contributions to synthetic organic chemistry, which is mainly concerned with makingnovelcompounds.Basedonthisanalysis,theauthormovesawayfromthe traditional hierarchical vision of the sciences and promotes a pluralistic vision, in terms ofboth interestsandcognitivetools. Inthefourthand closing chapterofthe first part, “The Elimination of the Holism-Reductionism Dichotomy Through the AnalysisofQuantumChemistry,”Jean-Pierre Llored appealstotheeffectivecom- putationalpracticeofquantumchemistrytoarguethattheusualholism-reductionism dichotomy is superseded by that very practice: the different types of calculation carried out in the field show not only the interdependence and codetermination of parts and wholes,but also theessential role played by the environment inthe very definitionofthesystemsunderstudy. Part II, “Models in Quantum Chemistry,” is composed of two chapters that analyze,from different perspectives, thecentralrole played byscientificmodels in quantumchemistry.Thechapter“ModelsandIdealizationsinQuantumChemistry: The Case of the Born-Oppenheimer Approximation,” by Juan Camilo Martínez x Introduction González andHernánAccorinti, isdevotedto analyzing different classificationsof idealizations proposed in the philosophical literature. The aim of the authors is to show that the Born-Oppenheimer approximation (which strictly speaking is not an approximation but an idealization) cannot be comfortably subsumed under those traditional schemes: it requires a refinement or enrichment of the existing classifi- cations.Inthefollowingchapter,“DoMoleculesHaveStructureinIsolation?How ModelsCanProvidetheAnswer,”VanessaA.Seifertdistinguishesbetweenmodels of isolated molecules and models of molecules in interaction. The former need to appeal to the Born-Oppenheimer approximation to identify molecular structure, since without it, the isolated molecule has no structure; the latter do not need to appeal to the Born-Oppenheimer approximation since non-isolated molecules can acquire their structure as a consequence of being embedding into a surrounding medium. These two chapters, although focusing on the use of models in quantum chemistry,openthewaytothediscussionsofthethirdpartofthevolume. Part III, “Quantum Chemistry and Quantum Mechanics,”with itsfour chapters, tacklesdirectlytheissueoftheinter-theoryandinter-disciplinarylinksinvolvedin quantum chemistry. In the first chapter of this part, “Quantum Mechanics and Molecular Structure,” Robin Findlay Hendry examines the relationship between quantummechanicsandthechemicalconceptsofmolecularstructureandchemical bond.Onthisbasis,theauthorrejectsthereductionistapproach,accordingtowhich physical facts ontologically determine all the chemical facts, and advances an emergentist view of that relationship, since it is better aligned with the role of quantum mechanics in chemistry. The following chapter, “Is Chemistry Really Founded in Quantum Mechanics?,” by Brian Sutcliffe and R. Guy Woolley, is a verydetailedandscientificallyinformeddiscussionofthesubtletiesinvolvedinthe useof quantummechanics intheoretical chemistry. The authorsstress that evenin computationalquantumchemistry,calculationsfordescribingmoleculesareaccom- plished by first clamping the nuclei at fixed positions, and this strategy leads to results that lack the symmetries of the full-quantum problem; on this basis, they conclude that, at present, molecules’ nuclear structure still needs to be put in by hand.Thepurposeofthethirdchapterofthispart,“AbouttheNatureoftheWave Function and its Dimensionality: The case of Quantum Chemistry,” by Sebastian FortinandJesúsA.JaimesArriaga,istofacetheproblemposedbythefactthatthe quantumwavefunctionisdefinedonaspaceof3Ndimensions(withNthenumberof particles),whereasthedescriptionsinquantumchemistryareframedinthephysical 3-dimensional space. By focusing on the so-called “independent electron approxi- mation,” the authors claim that the concept of orbital is not a mere approximation thatcouldberemovediftheexactsolutionwereaccessible,butitplaysanessential roleinquantumchemicalexplanations.Finally,inthechapter“CoarseGrainingand the Quantum Theory of Atoms in Molecules,” which closes the third part and the volume, Olimpia Lombardi and Chérif F. Matta address the nature of the electron densityinthecontextoftheQuantumTheoryofAtomsinMolecules(QTAIM).By showing that the electron density is a coarse-grained magnitude when considered fromtheviewpointofquantummechanics,theauthorsclaimthatthewayinwhich
The list of books you might like
