Table Of ContentNanostructure Science and Technology
SeriesEditor:
DavidJ.Lockwood,FRSC
NationalResearchCouncilofCanada
Ottawa,Ontario,Canada
Forfurthervolumes:
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Marcelo Mario Mariscal • Oscar Alejandro Oviedo
Ezequiel Pedro Marcos Leiva
Metal Clusters
and Nanoalloys
From Modeling to Applications
123
MarceloMarioMariscal OscarAlejandroOviedo
INFQC-CONICET INFQC-CONICET
UniversidadNacionaldeCo´rdoba UniversidadNacionaldeCo´rdoba
Co´rdoba Co´rdoba
Argentina Argentina
EzequielPedroMarcosLeiva
INFQC-CONICET
UniversidadNacionaldeCo´rdoba
Co´rdoba
Argentina
ISSN1571-5744
ISBN978-1-4614-3267-8 ISBN978-1-4614-3643-0(eBook)
DOI10.1007/978-1-4614-3643-0
SpringerNewYorkHeidelbergDordrechtLondon
LibraryofCongressControlNumber:2012938545
©SpringerScience+BusinessMediaNewYork2013
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Preface
Exceeding the limits of the academic realm where it started, the “nanowave” or
currentnanotechnologytrend,hasalreadyreachedtheindustrialandgovernmental
markets and nanotechnology has thus become a key area of public interest,
sincenotonlyresearchers—butalsopoliticiansandeconomists—haverealizedthe
social and economic implications of the developmentsin this field. In fact, Think
nano to earn giga will probably become one of the favorite expressions in the
businessworldinthefuture,asitiswidelyacceptedthat—aftermicrotechnology—
nanotechnologyisthetechnologyofthenextcentury.Metallicandsemiconducting
nanoparticles—subject of the present book—currently represent one of the most
tangibleapplicationsinnanotechnology.
From the point of view of academic research, nanoparticles show remarkable
propertiesduetothetransitionfromtheatomicquantummechanicalbehaviortothe
classicalbehaviorwhichgovernsbulkmaterials,makingthemidealcandidatesfor
testinganddevelopingnewtheories.
Inparticular,metallicnanoparticlesseemtobepromisingmaterialsforpotential
applicationsinvarioustechnologicalareasrelatedtodifferentspheresofhumanlife
rangingfromcatalysisofchemicalreactionstocancerdetectionandhealing
Asitusuallyhappensincasesofhastytechnologicaldevelopments,theurgefor
generatingthese new nanomaterialsis so strong that in many cases things are put
to work—and they work pretty well!—without much wondering about the subtle
reasons behind such results. After all, life evolution, a typical nanophenomenon,
just happened that way. This lack of modeling of nanophenomena—ascompared
totheabundantexperimentalresearch—isofcoursenotonpurpose,butratherthe
resultoftheintrinsiccomplexityofmodelingsystemsandsituationswherechemical
and physical phenomenaare strongly entangled. For instance, light absorption by
nanoparticles,atypicalphysicalphenomenon,maybefoundtobestronglymodified
bythechemicalnatureofmoleculeschemicallyboundtothem.Thus,thequantum
physical tools usually used to study the collective excitation of electrons in a
metal must be coupled with the quantum chemical tools that describe binding in
molecules,achallengeaddressedinthisbook.
v
vi Preface
Awakeningtheinterestofexperimentalresearchersinthenewestmodelingtools
appliedtometalnanoparticlesisoneofthemaingoalsofthepresentbook.Thus,in
tenchapterswrittenbyexpertsinthefieldwepresentthemostadvancedtechniques
employed to model and simulate metallic nanoparticles, with emphasis on their
applicationtoexperimentalresults.Thesetoolsrangefromstatisticalmechanicsand
moleculardynamicsimulationstoveryspecificquantummechanicalcalculations.
Since many of the topics represent cutting edge research developments, we
hope this work will help fill the existing gap between theory and experiment of
nanosystems,promotingfruitfulexchangesbetweenbothapproaches.
Co´rdoba,Argentina MarceloMarioMariscal
OscarAlejandroOviedo
EzequielPedroMarcosLeiva
Contents
PartI Recent Advances in High Resolution Electron
Microscopy
1 Experimental and Simulated Electron Microscopy
intheStudyofMetalNanostructures.................................... 3
SergioMej´ıa-RosalesandMiguelJose´-Yacama´n
PartII ElectronStructure,Optics,andMagnetism
2 Density-FunctionalTheoryofFreeandSupportedMetal
NanoclustersandNanoalloys.............................................. 29
AlessandroFortunelliandGiovanniBarcaro
3 Closed-ShellMetalClusters............................................... 81
Rene´FournierandSatyaBulusu
4 Optical Properties of Metal Nanoclusters from an
AtomisticPointofView.................................................... 105
ChristianF.A.NegreandCristia´nG.Sa´nchez
5 Spin-FluctuationTheoryofClusterMagnetism ........................ 159
R.Garibay-Alonso,J.Dorantes-Da´vila,andG.M.Pastor
PartIII ThermodynamicsandKineticsUsingSemiempirical
Approaches
6 GlobalOptimizationofFreeandSupportedClusters.................. 195
RiccardoFerrando
7 StructureandChemicalOrderinginNanoalloys:Toward
NanoalloyPhaseDiagrams................................................ 215
ChristineMottet
vii
viii Contents
8 ModellingJanusNanoparticles........................................... 243
FrancescaBaletto
9 ModelingofProtectedNanoparticles..................................... 275
JimenaA.Olmos-AsarandMarceloM.Mariscal
10 ThermodynamicModelingofMetallicNanoclusters................... 305
OscarA.OviedoandEzequielP.M.Leiva
Index............................................................................... 351
Part I
Recent Advances in High Resolution
Electron Microscopy
Chapter 1
Experimental and Simulated Electron
Microscopy in the Study of Metal
Nanostructures
SergioMej´ıa-RosalesandMiguelJose´-Yacama´n
1.1 Introduction
One of the most exciting features of nanostructuresrelays on the fact that matter
organized as objects at the nanoscale may have chemical and physical properties
differentfromthoseofthesamematerialinitscommonbulkpresentation.Thissize-
dependentpropertiesare related to several physical phenomena,such as quantum
behavior, high surface-to-volume ratio, and thermal effects [1,2]. Far from being
an unfortunate fact, the unique properties of nanostructures may in principle be
fine-tunedtobeusedforaspecificpurpose,buttobeabletodominatematteratthis
rangeofsizes,highprecisiontoolsmustbeusedinordertoinvestigate,measure,and
modifythephysicalandchemicalcharacteristicsofthenanostructures.Theproblem
is similar to the one of constructing a phase diagram for the bulk materials, but
taking also into consideration size and shape, besides temperature and crystalline
structure.Severalgroupshaveconcentratedsomeoftheireffortstothistask(with
varyingdegreesofsuccess),buttheseattemptsareinherentlyincompleteor,atbest,
restrictedto onespecificmaterialandtoa narrowrangeofsizes andtemperatures
[3,4]. On the other hand, these studies are generally based either on theoretical
results or on indirect experimental measurements, and there is just a relatively
smallnumberofpapersthatconcentrateonfirst-handmeasurementsofthedetailed
crystal structure and local chemicalcomposition of the nanostructures.This is, to
certaindegree,understandable:Adetailedanalysisofthestructureandcomposition
S.Mej´ıa-Rosales((cid:2))
CenterforInnovationandResearchinEngineeringandTechnology,andCICFIM-Facultad
deCienciasF´ısico-Matema´ticas,UniversidadAuto´nomadeNuevoLeo´n,SanNicola´sdelos
Garza,NL66450,Me´xico
e-mail:[email protected]
M.Jose´-Yacama´n
DepartmentofPhysicsandAstronomy,UniversityofTexasatSanAntonio,
OneUTSACircle,SanAntonio,TX78249,USA
e-mail:[email protected]
M.M.Mariscaletal.,MetalClustersandNanoalloys:FromModelingtoApplications, 3
NanostructureScienceandTechnology,DOI10.1007/978-1-4614-3643-0 1,
©SpringerScience+BusinessMediaNewYork2013
