MOLECULAR MODELING OF CORROSION PROCESSES THEELECTROCHEMICALSOCIETYSERIES Acompletelistofthetitlesinthisseriesappearsattheendofthisvolume. MOLECULAR MODELING OF CORROSION PROCESSES Scientific Development and Engineering Applications Edited by CHRISTOPHER D. TAYLOR Strategic Research& Innovation, DNV GL,Dublin,OH,USA Fontana Corrosion Center, Department of Materials Science and Engineering, The Ohio State University, Columbus, OH, USA PHILIPPE MARCUS Institut de Recherche de Chimie Paris/Physical Chemistry of Surfaces,Chimie ParisTech-CNRS,EcoleNationaleSupérieuredeChimiedeParis,Paris,France Copyright©2015byJohnWiley&Sons,Inc.Allrightsreserved PublishedbyJohnWiley&Sons,Inc.,Hoboken,NewJersey PublishedsimultaneouslyinCanada Nopartofthispublicationmaybereproduced,storedinaretrievalsystem,ortransmittedinanyformorby anymeans,electronic,mechanical,photocopying,recording,scanning,orotherwise,exceptaspermitted underSection107or108ofthe1976UnitedStatesCopyrightAct,withouteitherthepriorwrittenpermission ofthePublisher,orauthorizationthroughpaymentoftheappropriateper-copyfeetotheCopyrightClearance Center,Inc.,222RosewoodDrive,Danvers,MA01923,(978)750-8400,fax(978)750-4470,orontheweb atwww.copyright.com.RequeststothePublisherforpermissionshouldbeaddressedtothePermissions Department,JohnWiley&Sons,Inc.,111RiverStreet,Hoboken,NJ07030,(201)748-6011,fax(201) 748-6008,oronlineathttp://www.wiley.com/go/permissions. 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Wileyalsopublishesitsbooksinavarietyofelectronicformats.Somecontentthatappearsinprintmay notbeavailableinelectronicformats.FormoreinformationaboutWileyproducts,visitourwebsiteat www.wiley.com. LibraryofCongressCataloging-in-PublicationData: Molecularmodelingofcorrosionprocesses:scientificdevelopmentandengineeringapplications/ editedbyChristopherD.Taylor,PhilippeMarcus. pages cm Includesindex. ISBN978-1-118-26615-1(cloth) 1. Corrosionandanti-corrosives. 2. Corrosionandanti-corrosives–Mathematicalmodels. I. Taylor,ChristopherD.,1978–editor. II. Marcus,P.(Philippe),1953–editor. TA418.74.M6562015 620.11223–dc23 2015000031 Setin9.5/11.5ptTimesbySPiPublisherServices,Pondicherry,India PrintedintheUnitedStatesofAmerica 10 9 8 7 6 5 4 3 2 1 1 2015 CONTENTS ListofContributors vii Foreword ix Preface xi 1 AnIntroductiontoCorrosionMechanismsandModels 1 ChristopherD.Taylor,JulianD.Gale, Hans-HenningStrehblowandPhilippeMarcus 2 MolecularModelingofStructureandReactivityatthe Metal/EnvironmentInterface 35 ChristopherD.Taylor 3 ProcessesatMetal–SolutionInterfaces:Modeling andSimulation 65 NoeliaB.Luque,WolfgangSchmickler,ElizabethSantos andPaolaQuaino 4 AtomisticMonte-CarloSimulationsofDissolution 99 StevePolicastro 5 AdsorptionofOrganicInhibitorMoleculesonMetalandOxidized SurfacesstudiedbyAtomisticTheoreticalMethods 125 DominiqueCostaandPhilippeMarcus 6 ThermodynamicsofPassiveFilmFormationfrom FirstPrinciples 157 MichaelF.FrancisandEdwardF.Holby vi CONTENTS 7 PassiveFilmFormationandLocalizedCorrosion 191 VincentMaurice,AlexisMarkovits,ChristianMinot andPhilippeMarcus 8 MultiscaleModelingofHydrogenEmbrittlement 223 XuZhangandGangLu Index 251 LIST OF CONTRIBUTORS DominiqueCosta, InstitutdeRecherchedeChimieParis/PhysicalChemistryofSurfaces, ChimieParisTech-CNRS,EcoleNationaleSupérieuredeChimiedeParis,Paris,France Michael F. Francis, École Polytechnique Fédérale de Lausanne (EPFL), STI IGM LAMMM,Lausanne,Switzerland BrownUniversity,SchoolofEngineering,Providence,RhodeIsland,USA Julian D. Gale, Department of Chemistry, Nanochemistry Research Institute, Curtin University,Perth,WA,Australia Edward F. Holby, Materials Science and Technology Division, MST-6, Los Alamos NationalLaboratory,LosAlamos,NM,USA GangLu, DepartmentofPhysicsandAstronomy,CaliforniaStateUniversityNorthridge, Northridge,CA,USA NoeliaB.Luque, InstituteofTheoreticalChemistry,UlmUniversity,Ulm,Germany PhilippeMarcus, InstitutdeRecherchedeChimieParis/PhysicalChemistryofSurfaces, ChimieParisTech-CNRS,EcoleNationaleSupérieuredeChimiedeParis,Paris,France AlexisMarkovits, LaboratoiredeChimieThéorique,UniversitéPierreetMarieCurie— CNRS,Paris,France VincentMaurice, InstitutdeRecherchedeChimieParis/PhysicalChemistryofSurfaces, ChimieParisTech-CNRS,EcoleNationaleSupérieuredeChimiedeParis,Paris,France Christian Minot, Laboratoire de Chimie Théorique, Université Pierre et Marie Curie— CNRS,Paris,France Steve Policastro, Center for Corrosion Science and Engineering, Chemistry Division, NavalResearchLaboratory,Washington,DC,USA PaolaQuaino, PRELINE,UniversidadNacionaldelLitoral,SantaFé,Argentina ElizabethSantos, InstituteofTheoreticalChemistry,UlmUniversity,Ulm,Germany FaculdaddeMatemática,AstronomíayFísica,IFEG-CONICET,UniversidadNacional deCórdoba,Córdoba,Argentina WolfgangSchmickler, InstituteofTheoreticalChemistry,UlmUniversity,Ulm,Germany viii LISTOFCONTRIBUTORS Hans-Henning Strehblow, Institute of Physical Chemistry, Heinrich-Heine-Universität, Düsseldorf,Germany ChristopherD.Taylor, StrategicResearch&Innovation,DNVGL,Dublin,OH,USA FontanaCorrosionCenter,DepartmentofMaterialsScienceandEngineering,TheOhio StateUniversity,Columbus,OH,USA XuZhang, DepartmentofPhysicsandAstronomy,CaliforniaStateUniversityNorthridge, Northridge,CA,USA