CrystallineLattice (Ch1&2ofCMP)

BravaisLatticeandPrimitiveVectors UnitCells CrystalStructures Symmetries:spacegroupandpointgroup ClassificationofLatticesbySymmetry

Crystallinesolids
Crystallineorderisthesimplestwaythatatomscouldbepossiblybe arrangedtoformamacroscopicsolid.

Foralmostalltheelementsand foravastarrayofcompounds, thelowestenergystateis crystalline,exceptforhelium whichremainsliquidatzero 1st published naturally occurring temperatureandstandard picture of a crystals of iron pyrite. pressure. crystal structure (minerals consisting of
iron disulfide)

Whyarelowenergyarrangementsofsomeatomssooftenperiodic? Noonereallyknows.

CrystallineLattice:repeatingoverandover
Afundamentalconceptinthedescriptionofanycrystallinesolidis theBravaislattice,acollectionofpointsinwhichtheneighborhood ofeachpointisthesameastheneighborhoodofeveryotherpoint undersometranslation. i.e.,arepeatedarrayofpointswithan , arrangementandorientationthatappearsexactlythesame,from whicheverthepointsofthearrayisviewed. Thelocationofverypointinsuch alatticecandescribedintheform
R = n1a1 + n2 a2 + n3a3 ,
al wherearecalledprimitivevectors, also called a triangular lattice, andmustbelinearlyindependent. symmetric under reflection about x
& y axes, and 60-rotation
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Intwodimensions,thereare5Bravaislattices.
symmetric under reflection about x & y axes, and 90-rotation a compression of the hexagonal lattice without the 60 rotational symmetry.

a square lattice losing the 90 rotational symmetry. arbitrary choice of a1 and a2 with no special symmetry, still possessing inversion symmetry.
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Areprimitivevectorsunique? No,forhexagonallattice.

However,onecouldequally choose

Cana latticeofafivefoldrotationalsymmetryexist?

ConsideratwodimensionalBravais latticethatisinvariant underarotation aroundtheorigin.

(a cos , a sin ) isaBravais latticepointwithabeingalattice

constant,andthereisarotationsymmetryof, (a cos , a sin ) mustbeaBravais latticepoint.

(a cos , a sin )

(0, 2a sin ) HenceisaBravais latticepoint, (0, 2sin ) = (cos , sin ) (cos , sin )

Onotherhand,ifwechoosetheprimitivevectorsas a1 = (a, 0) a2 = (a cos , a sin )

(0, 2a sin ) = n1 (a,0) + n2 (a cos , a sin ) n1 + 2cos = 0;

(a, 0)

n2 = 2

cos = integer / 2

2 2 2 2 2 , , , , = 0, 2 3 4 5 6

ItisimpossibleforaBravais latticetoafivefoldrotationaxis.
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UnitCells
Becauselatticesarecreatedbyrepeatingbasicunitsoverandover throughoutspace,thefullinformationofacrystalcanbeobtainedin asmallregionofspace.Sucharegion,chosentobeassmallasitcan be,iscalledprimitiveunitcell. Primitivecell:avolumeofspacethat,whentranslatedthroughall thevectors inaBravaislattice,justfillsallofspacewithouteither overlappingitselforleavingvoids. Eachprimitivecellcontains onlyonlatticepoint. Primitivecellsarenotunique.

Onecanalsofillspaceupwithnonprimitivecells(knownas conventionalcells).Theconventionalunitcell isaregionthat justfillsspacewithoutanyoverlappingwhentranslated throughsomesubsetofthevectorsofaBravaislattice. Theconventionalunitcellisgenerallychosentobebiggerthan aprimitivecellandtohavetherequiredsymmetry. WignerSeitzcell: aprimitivecellwithfull symmetryoftheBravaislattice.Thecellabouta latticepointistheregionofspacethatiscloserto anyotherlatticepoint. TheWignerSeitzcellcanbe constructedbydrawingthe perpendicularbisectorofallthelines betweenalatticepointtoeachofits neighbor.
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CrystalStructure:latticewithabasis
Acrystalstructureconsistsofidenticalcopiesofthesamephysical unit,calledthebasis,locatedatallthepointsofaBravaislattice. Forexample,a2Dhoneycomb,thoughnot aBravaislattice,canbe constructedbyatriangular(hexagonal)Bravaislattice. Primitivevectors
a1 = ( a2 = ( 3 1 , )a 2 2 3 1 , )a 2 2

triangularlattice

notinvariantunder reflection

Theleftandrightparticlesineach cellfindtheirneighborsoffat differentsetsofangles.

basisparticles 1 at v1 = ( 2 3 , 0)a
v1 = ( 1 , 0)a 2 3

Onceonedecoratesalatticewithabasis,itssymmetriesmight change. Ingeneral,thesessymmetriesofalatticecanbedestroyedby addingbasiselements. Inatriangularlatticedecoratedwith chiralmolecules,therotational symmetries oftheoriginallatticeare preserved,butnotthereflection symmetry. Anobjectorasystemiscalledchiral if itdiffersfromitsmirrorimage,andits mirrorimagecannotsuperimposeon theoriginalobject. Anonchiralobject iscalledachiral andcanbe superimposedonitsmirrorimage.
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Introductiontogrouptheory
Ref:M.Tinkham,GroupTheoryandQuantumMechanics

Agroupissetofelements A, B, C..suchthataformofgroup multiplicationsatisfiestherequirements: Theproductofanytwoelementsisintheset. Theassociativelawholds;e.g.,A(BC)=(AB)C. ThereisaunitelementE suchthatEA=AE=A. Thereisaninverse A-1 ofeachelementA suchthatAA-1=A-1A=E. Crystalsymmetryoperationssuchastranslation,rotation,reflection, inversion,canformagroup.

Forexample,allrotationsbyn/3 (n=0,1,2,5) aboutsomeaxisform agrouptermedC6. Insuchagroup, (1) themultiplicationAB meanstherotationfirstbyB,thenA. (2) theunitelementisnooperationatall. (3) Theinverseoperationisarotationthesameangleinreversesense.
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Thespacegroup oftheBravaislattice:acompletesetofallrigid bodyoperationcomposedofatranslationandarotation.

G = a + R (n, )

There are 230 space groups and 32 point groups in three dimensions.

Thepointgroup oftheBravaislattice:asubsetofthefullsymmetry group,leavingaparticularpointfixed,e.g.,C6. Notethatthepointgroupofalatticecannotdefinethelattice, becausedifferentlattices,suchasrectangularandcentered rectangular,canbeinvariantunderpreciselythesamesetofpoint symmetryoperations. Althoughrectangularandcenteredrectangularlatticesshare pointgroupsymmetries,theyhavedifferentspacegroupsand aredifferentlattices.

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Notonlyforclassifyingcrystalstructures,thesymmetryofcrystal canefficientlyreducethecomputationeffort insolvingthe Schrodingersequationinperiodicpotentials, andleadto significantpredictionsofthesolutions.Symmetriesalsoprovide uswithqualitativeinformation. Forexample,withpracticallynoworkatall,onecanuse symmetriestoidentifyplacesinkspacewhereenergybandswill bedegenerate. Inthreedimensions,Thereareonly7distinctpointgroupsthata Bravaislaticecanhave.Outofthese,thereare14differentkindsof Bravaislattice.

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bcc

(trigonal)

bct

fcc
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Schnfliesnonation Cn: Cyclic,groupshavingonlyone nfoldrotationaxis Dn: Dihedral,groupshavingn 2fold rotationaxis totheprincipalCn axis. Additionalsymbolsformirrorplanes: h, v, d h: horizontal= totherotationaxis v: vertical=// therotationaxis d: diagonal=// themainrotationaxis intheplaneandbisectingtheangle betweenthe2foldaxes tothe principalaxis.

C4

Sn: Spiegel (German for mirror), containing nfold axisforimproperrotation(rotoinversion),i.e., acombinationofarotationandaninversion inapointontheaxis O: Octahedral,thegroupof24proper rotationswhichtakeanoctahedron (orcube)intoitself. 8C3 T: Tetrahedral,thegroupof12proper rotationswhichtakearectangular tetrahedronintoitself.
6C4, 3C2

S4

6C2

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Usingaprojectiontorepresenta3Dcrystal on2Dplane: Stereographicprojections

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Stereographicprojections ofthe32crystallographic pointgroups

SomeImportantandPopularCrystalStructures
HexagonalClosePackedLattice: Astackingof2Dtriangularlattices, ahexagonallatticewithtwopoint a a c , ) basis:(0,0,0)and ( 2 , 2
2 3

Thestructureisclosepackif (Homework:Problem2.4)

c 8 = a 3

Diamondstructure: Afcclatticewithtwo pointbasis:(0,0,0)and (1/4,1/,4,1/4)a

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Rocksalt(SodiumChloride) AfcclatticewithNaat(0,0,0)and Clat(1/2,0,0)a.

CsClstructure: AbcclatticewithCsat(0, 0,0)andClat(1/2,1/2, 1/2)a.

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Zincblende(ZnS)structure: identicaltodiamond,except thattwospeciesofatoms alternatebetweensites.

O Ca

Ti

Perovskite(CaTiO3)structure: Ca:asimplecubiclattice. Ti:atthebodycenter O:onthefacecenters.

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