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InteratomicBondinginMaterials

TeachingPlan:
InteratomicBonds

ChemicalBondinginSolids

2h

2h

0h

Assignment:

TableofContents

1 InteratomicBonds
1.1 PrimaryandSecondarybonding

1.1.1
1.1.2
1.1.3
1.1.4

LenardJonesPotential
Primarybonding:Ionic,covalentandmetallicbonding
Secondarybonding:Permanentdipoleandfluctuatingdipole
Mixedbonding

1 InteratomicBonds
Thewaytheatomsbindtogethertoformasolidisofextremeimportancesincethetypeofbonding
is the crucial ingredient to determine the crystalline structure and consequently the properties of
thematerial.Generallyspeaking,whentwoisolatedatomsarebroughtclosetoeachother,their
valence electrons interact with each other as well as with the nucleus of the neighbouring atom.
Such interaction results in the formation of bond between the two atoms provided that such
formationofbondisenergeticallyfavourable.Withthatwhatismeantisthatiftwoisolatedatoms,
AandB,forinstance,arebroughtinsufficientproximity,theformationofabondbetweenthemwill
be governed by the condition that EAB EA + EB; where EAB, EA and EB are energy of AB molecule,
energyofAatomandenergyofBatom,respectively.
Alittlemoreinspectionintotheelectronicstructureofelementsfurtherrevealsthatitisa
natural tendency for all elements to try and attain stable electronic configuration (those of noble
gases)toreachtheminimumenergyconfiguration.Elementswithpartiallyfilledorbitalsistherefore
eagertoachievetheclosestnoblegas electronic configuration eitherbyleaving/addingorsharing
electron(s) of their outer most shell. On the other hand, atoms with closed shell structure
experiences weak vanderWaals force which brings them in sufficient proximity to form bond at
sufficientlylowtemperature.Inallcasestheoverallpotentialenergyofthesystemislowered.
Theinteratomicbondsmentionedabove,thus,couldbestrong,whichgivesrisetoprimary
bondsandcouldbeionic,covalent,ormetallicinnature.UsuallyvanderWaalsandhydrogenbonds
are referred to as secondary bonds and are weaker. In all cases, however, it is the attractive

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electrostaticinteractionbetweenthepositivechargesofthenucleiandthenegativechargesofthe
electronsthatisresponsibleforthecohesionofsolids.

Keywords:Drivingforceforchemicalbondingisenergyminimization.

1.1 BondingForcesandBondingEnergy
Letusconsidertheinteractionbetweentwoisolatedatomsastheyarebroughtintocloseproximity
from an infinite separation. At large distances, the interactions are negligible, but as the atoms
approach,eachexertsforcesontheother.Theseforcesareoftwotypes,attractiveandrepulsive,
andthemagnitudeofeachisafunctionoftheseparationorinteratomicdistance.Theoriginofan
attractiveforceFAdependsontheparticulartypeofbondingthatexistsbetweenthetwoatoms.The
magnitude of the attractive force varies with the distance, as represented schematically in Figure
1.1a.Ultimately,theouterelectronshellsofthetwoatomsbegintooverlap,andastrongrepulsive
force FR comes into play owing to Paulis exclusion principle. The net force FN between the two
atomsisjustthesumofbothattractiveandrepulsivecomponents;thatis,
FN=FA+FR
whichisalsoafunctionoftheinteratomicseparation,asalsoplottedinFigure1.1a.WhenFAandFR
balance,orbecomeequal,thereisnonetforce;thatis,
FA+FR=0

(1.1)
and a state of equilibrium exists. The centers of the two atoms will remain separated by the
equilibriumspacingr0,asindicatedinFigure1.1a.Formanyatoms,r0isapproximately0.3nm.Once
inthisposition,thetwoatomswillcounteractanyattempttoseparatethembyarepulsiveforce,or
topushthemtogetherbyanattractiveaction.
Sometimesitismoreconvenienttoworkwiththepotentialenergiesbetweentwoatoms
insteadofforces.Mathematically,energy(E)andforce(F)arerelatedas:

(1.2)

in which EN, EA, and ER are respectively the net, attractive, and repulsive energies for two isolated
andadjacentatoms.Figure1.1(b)plotsattractive,repulsive,andnetpotentialenergiesasafunction
ofinteratomicseparationfortwoatoms.Thenetcurve,whichisagainthesumoftheothertwo,has
apotentialenergytrougharounditsminimum.Here,thesameequilibriumspacing,r0,corresponds
to the separation distance at the minimum of the potential energy curve. The bonding energy for
thesetwoatoms,E0,correspondstotheenergyatthisminimumpoint(alsoshowninFigure1.1b);it
representstheenergythatwouldberequiredtoseparatethesetwoatomstoaninfiniteseparation.
Although the preceding treatment has dealt with an ideal situation involving only two atoms, a
similaryetmorecomplexconditionexistsforsolidmaterialsbecauseforceandenergyinteractions
among many atoms must be considered. Nevertheless, a bonding energy, analogous to E0 above,
may be associated with each atom. The magnitude of this bonding energy and the shape of the
energyversusinteratomicseparationcurvevaryfrommaterialtomaterial,andtheybothdependon
thetypeofatomicbonding.Furthermore,anumberofmaterialpropertiesdependonE0,thecurve
shape,andbondingtype. Forexample,materialshavinglargebondingenergiestypicallyalsohave
high melting temperatures; at room temperature, solid substances are formed for large bonding
energies,whereasforsmallenergiesthegaseousstateisfavoured;liquidsprevailwhentheenergies
are of intermediate magnitude. In addition, mechanical stiffness (or modulus of elasticity) of a
materialisdependentontheshapeofitsforceversusinteratomicseparationcurve.Theslopefora
relativelystiffmaterialatther=r0positiononthecurvewillbequitesteep;slopesareshallowerfor

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moreflexiblematerials.Furthermore,howmuchamaterialexpandsuponheatingorcontractsupon
cooling(thatis,itslinearcoefficientofthermalexpansion)isrelatedtotheshapeofitsE0versusr0
curve. A deep and narrow trough, which typically occurs for materials having large bonding
energies, normally correlates with a low coefficient of thermal expansion and relatively small
dimensionalalterationsforchangesintemperature.

Keywords: (i) Equilibrium bond length is determined by zero force/lowest potential energy
configuration.
(ii)Shallowtroughinpotentialenergyplot,indicatesweakbonding.Narrowanddeep
troughmeansstronginteratomicbond

Fig.1.1(a)

1.2 TypesofBonding
Dependingonthemagnitudeoftheinteratomicbondstrength,chemicalbondinginmaterialscould
be broadly divided into two categories: (i) Primary bonding and (ii) Secondary bonding. Primary
bonds,whereinrelativelylargeinteratomicforcesdevelopcan befurtherdividedintothreemajor
classesionic, covalent, and metallic. For each type, the bonding necessarily involves the valence
electrons; furthermore, the nature of the bond depends on the electron structures of the
constituentatoms.Ingeneral,eachofthesethreetypesofbondingarisesfromthetendencyofthe
atoms to assume stable electron structures, like those of the inert gases, by completely filling the
outermost electron shell. Secondary or physical forces and energies are also found in many solid
materials;theyareweakerthantheprimaryones,butnonethelessinfluencethephysicalproperties
of some materials. Following sections explain several kinds of primary and secondary interatomic
bonds.

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1.2.1 PrimaryBonding
1.2.1.1 IonicBondingandIonicallyBondedSolids
Ionicbondingisperhapstheeasiesttodescribeandvisualize.Ionicbondsgenerallyformbetween
veryactivemetallic(electropositive)elementsandactivenonmetals(electronegative).Forreasons
thatwillbecomeclearshortly,therequirementsforanABionicbondtoformarethatAbeableto
loseelectronseasilyandBbeabletoacceptelectronswithouttoomuchenergyinput.Thisrestricts
ionicbondingtomostlymetalsfromgroupsIA,IIA,andpartofIIIAaswellassomeofthetransition
metalsandthemostactivenonmetalsofgroupsVIIAandVIA.Therefore,elementsthataresituated
atthehorizontalextremitiesoftheperiodictablearecandidatestoformionicbonding.Inthebond
formation,atomsofametallicelementgiveuptheirvalenceelectronstothenonmetallicatoms.In
the process all the atoms acquire stable or inert gas configurations and, in addition, an electrical
charge;thatis,theybecomeions.

Keywords: ionic bonding occurs between highly electropositive and highly electronegative
elements.
ToillustratetheenergeticsofionicbondingconsiderthebondformedbetweenNaandCl.
TheelectronicconfigurationofCl(atomicnumberZ=17)is[1s22s22p6]3s23p5,whilethatofNa(Z=
11) is [1s22s22p6]3s1. When a Na and a Cl atom are brought into close proximity, a bond will form
(thereasonwillbecomeevidentinamoment)bythetransferofanelectronfromtheNaatomto
theClatom,asshownschematicallyinFig.2.3.TheNaatomconfigurationbecomes[1s22s22p6]and
is now +1 positively charged. The Cl atom, however, gains an electron, acquires a net negative
charge with an electronic structure [1s22s22p6]3s23p6, and is now an anion. Note that after this
transferofcharge,theconfigurationofeachoftheionscorrespondstothoseofthenoblegases,Ne
andAr,respectively.

(a)

(b)

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(c)
Fig.1.2.

TheworkdonetobringtheionsfrominfinitytoadistancerapartisonceagaingivenbyCoulomb's
law:

(1.3)

Inthiscase,Z1andZ2arethenetchargesontheions(+1and1forNaCl,2and+3forA12O3,
etc.),eiselectronicchargeand0isfreespacepermittivity(0=8.851012F/m).WhenZ1andZ2are
ofoppositesigns,EAisnegative,whichisconsistentwiththefactthatenergyisreleasedastheions
arebroughttogetherfrominfinity.AplotofEq.(1.14)isshowninFig.1.7(lowerplot),fromwhichit
is clear that when the ions are infinitely separated, the interaction energy vanishes, as one would
expect. Equation (1.14) also predicts that as the distance between the ions goes to zero, the ions
shouldfusetogetherandreleaseaninfiniteamountofenergy!Thatthisdoesnothappenisobvious.
Itfollowsthatforastablelatticetoresult,arepulsiveforcemustcomeintoplayatshortdistances.
Asdiscussedabove,theattractionoccursfromthenetchargesontheions.Theseions,however,are
themselves made up of positive and negative entities, namely, the nuclei of each ion, but more
importantly, the electron cloud surrounding each nucleus. As the ions approach each other, the
electron clouds start overlapping and due to Paullis exclusion principle (two electrons with same
spincannotoccupysameenergystate)arepulsiveforcecomesintoplaywhichwouldpreventthe
ions from coming further closer. The repulsive energy term is positive by definition and is usually
givenbytheempiricalexpression:

(1.4)
whereBandnareempiricalconstantsthatdependonthematerialinquestion.Sometimesreferred
toastheBornexponent,nusuallyliesbetween6and12.Equation(1.15)isalsoplottedinFig.1.7,
fromwhichitisclearthattherepulsivecomponentdominatesatsmallrbutdecreasesveryrapidly
asrincreases.ThenetenergyENofthesystemisthesumoftheattractiveandrepulsiveterms,or

(1.5)

WhenENisplottedasafunctionofr,itgoesthroughaminimum,atadistancedenotedbyr0.The
minimuminthecurvecorrespondingtotheequilibriumsituationcanbefoundreadilyfrom:
|

=0

(1.6)

ByevaluatingtheconstantBandremovingitfromEq.(1.17),itcanbeeasilyshownthatthedepth
oftheenergywellE0isgivenby:
1

(1.7)

where r0 is the equilibrium separation between the ions. The occurrence of this minimum is of
paramountimportancesinceitdefinesabond;i.e.whentwoionsarebroughtclosertogetherfrom
infinity, they will attract each up to an equilibrium distance r0 and liberate an amount of energy

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givenbyEq.(1.18).Conversely,Ebondcanbethoughtofastheenergyrequiredtopulltheionsapart.
ItisimportanttonotethatEq.(1.18)isalsoanexpressionforthenetforcebetweentheions,since
bydefinition:
.FNisplottedinFig.1.7.Fordistancesgreaterthanr0thenetforceonthe
ionsisattractive;andfordistanceslessthanr0;thenetforceisrepulsive.Atr0thenetforceonthe
ions is zero which is why r0 is the equilibrium interatomic spacing. Figure 1.7 illustrates a
fundamentallawofnature,namely,thatatequilibriumtheenergyisminimizedandthenetforceon
asystemiszero.
Thenextlogicalquestionis,howdosuchbondsleadtotheformationofasolid?Afterall,an
ionicsolidismadeupofroughly~1023ofthesebonds.Theotherrelatedquestionofimportancehas
todowiththeenergyofthelattice.Thisenergyisrelatedtothestabilityofagivenionicstructure
and directly or indirectly determines such critical properties as melting temperatures, thermal
expansion,stiffness,andothers.

1.2.1.1.1 LatticeEnergyCalculations
TheCoulombenergybetweentwoionswithchargesZ1andZ2andseparationris:

.But

astheCoulombforceisalongrangeforce,agivenioninteractswithnotjustthenearestneighbours
but with more distant neighbours too. Let us consider a linear one dimensional lattice which is a
chainofionswithalternatesigns(Fig.1.8),(letussay,Na+andClions)theseparationofeachion
from its neighbour being r0. Let us consider the positive ion at 0 as the reference ion. The net
potentialenergyofthereferenceionduetoseveralofitsneighboursis:

Fig.1.3.

4
2
4

1 2

1
1

2
2
1
1
1
2

2
2

3
4
1 1

3 4

(1.8)

wheretheconstantMiscalledtheMadelungconstant.Theseriesaddsupto2log2=1.38.
LetusnowconsidertheNaCllatticeinthreedimensions(Fig.1.9).Thedistancebetweenthe
referenceionatAanditsnearestneighbourisr0andthelatticeconstanta0=2r0.Thisreferenceion
Na+hasasitsneighbours6Clionsatdistancer0;12Na+ionsatdistance2r0;8Clionsatdistance
3r0,again6Na+ionsatdistance4r0,andsoon.ThetotalelectrostaticinteractionenergyEsumof
theNa+ionatAduetoalltheneighbouringionsis:

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Fig.1.4

4

1 6
1

12

(1.9)

The Madelung constant M of the NaCl lattice represented by the series above and has the value
1.747565.ThemagnitudeofMadelungconstantdependsuponthestructure.Physicallyitrepresents
theCoulombenergyofanionpairinacrystalrelativetotheCoulombenergyofanisolatedionpair.
The magnitude it greater than unity but remains close to it. The Madelung constants for some
commonionicstructuresaregiveninTable1.1.
Table1.1:

Thetotalelectrostaticattractionfor1moleofNaClinwhichtherearetwiceAvogadro'snumberNAv
ofionsbutonlyNAvbondsis:
.

(1.10)

According to this equation, sometimes referred to as the BornLande equation, the information
required to calculate Elatt is the crystal structure, which determines the equilibrium interionic
spacing, and n which is obtainable from compressibility data. Note that the lattice energy is not
greatlyaffectedbysmallerrorsinn.
In deriving Eq. (1.21), few terms were ignored. A more exact expression for the lattice
energyis:

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(1.11)

Thefirsttwoterms,whichhavebeendiscussedindetailuptothispoint,dominate.Notetheterm
z1z2e2/40inEq.(1.21)isaconstantreplacedbyAinEq.(1.22).Theterminparenthesesrepresents
dipoledipoleanddipolequadrapoleinteractionsbetweentheions.1Thelasttermrepresentsthe
zeropointcorrection,withvmaxbeingthehighestfrequencyofthelatticevibrationmode.
Thestrengthofionicbondsincreasesasthevalenceincreases.Theelectrondistributionin
ions is nearly spherical and the interatomic bond, since it arises from coulombic forces, is non
directionalinnature.The stablestructureassumedbyanioniccompoundthustendstobeonein
which an ion obtains the maximum number of neighbours (or, coordination number) of opposite
charge.Suchstructuresthereforedependonobtainingmaximumpackingdensityoftheions.
Ionic crystals are characterized by strong infrared absorption, transparency in visible
wavelengthsandlowelectricalconductivityathightemperatures.Compoundswithmetalionswith
group VII anions are strongly ionic. Compounds of metals with oxygen ions are largely ionic.
CompoundswithhigheratomicweightelementsofgroupVIwhichhavelowerelectronegativityare
increasinglylessionicincharacter.Finallyinthissectionitisworthnotingthatthisionicmodelisa
poor approximation for crystals containing large anions and small cations where the covalent
contributiontothebondingbecomessignificant.

Problems:
1. Calculatetheenergyrequiredtotake1molofsolidNaClapartintoindividualNaandCl
atoms.Assumerepulsionindex,n=10.
2. EstimatethecohesiveenergyofNaBrforwhichr0D2:989AandtheBornrepulsionindexis
8.
3. DerivetheMadelungconstantfortheCsClstructure.

Sol. 3. Madelung constants can be derived by calculating a summation of coulombic

interactions, each term in the series indicates all the interactions for a specific ion-ion
distance. For each term, the sign (from anion or cation), the total number of interactions, and
interaction distance needs to be determined. The notes have a simple example for the infinite
linear chain. Derive the first 30 terms (arising from 30 shortest distances) for determining the
Madelung constant of CsCl. For each term, indicate the number of interactions, the sign, and
the distance in terms of the lattice parameter a. To accomplish this, apply symmetry and
permutations to (xyz) coordinates, do not try to use drawings or models.
In the CsCl structure, if we put a Cl at the origin (000), then the lattice generation rules
are:
Cl at all sites (n, n, n) and Cs at all sites (n/2, n/2, n/2); where n is any integer (positive or
negative)
The distance from the origin is found from the coordinates by: distance = (x2 + y2 + z2)1/2
The number of ions at any given distance can be determined from all possible
permutations with the same distance, interchanging the coordinates and switching
positive and negative values. For example:
( ) has 8 permutations with the same distance: ( ), (- ), ( - ), (
-), (- - ), ( - -), (- -), (- - -)
(1 0 0) has 6: (1 0 0), (0 1 0), (0 0 1), (-1 0 0), (0 -1 0), (0 0 -1)
Any general coordinates (x y 0) will have 12 permutations if x = y, and 24 if x y
At most, the coordinates (x y z) where all are non-zero and x y z has 48 permutations.

SeeAnnex.Ifordetails

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The total energy contribution for the interactions at a particular distance will be
proportional to the number of interactions / distance.
Finally,notetheMadelungconstanttermisrelatedtod(theclosestapproachofions)
ratherthana(theunitcelledgelength).Inthiscell,d=0.866a,sowemultiplythetotal
energycontributionsbythisfactortogettheMadelungconstantterms.

1.2.1.2 CovalentBondingandCovalentlyBondedSolids
The second type of primary bonding is covalent bonding. While ionic bonding requires
involvementofhighlyelectropositiveandhighlyelectronegativeelements,covalentbonding
occurs between atoms with similar electronegativity with minor differences. In covalent
bonding,theatoms,ingeneral,sharetheiroutersandpelectronswithotheratomsofsame
ordifferentelement.Consequently,theatomsattainnoblegaselectronconfigurationsand
the system lowers the energy. In other words, bond formation is favoured. In a single
covalentbond,eachofthetwoatomscontributesoneelectrontoformanelectronpairand
theenergiesofthetwoatomsareloweredbecauseoftheaboveelectronicinteraction.In
covalent bonding, multiple electronpair bonds can be formed by one atom with itself or
otheratoms. Twoatoms thatare covalentlybondedwilleachcontributeatleastoneelectronto
thebond,andthesharedelectronsmaybeconsideredtobelongtobothatoms.
Covalent bonding is schematically illustrated in Figure 1.10 for a methane molecule. The
carbon atom has four valence electrons, whereas each of the four hydrogen atoms has a single
valenceelectron.Eachhydrogenatomcanacquireaheliumelectronconfiguration(two1svalence
electrons) when the carbon atom shares with it one electron. The carbon now has fouradditional
sharedelectrons,onefromeachhydrogen,foratotalofeightvalenceelectrons,andtheelectron
structure of neon. The covalent bond is directional; that is, it is between specific atoms and may
existonlyinthedirectionbetweenoneatomandanotherthatparticipatesintheelectronsharing.

Fig.1.5

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Manynonmetallicelementalmoleculesaswellasmoleculescontainingdissimilaratoms,suchasand
HF, are covalently bonded. Furthermore, this type of bonding is found in elemental solids such as
diamond(carbon),silicon,andgermaniumandothersolidcompoundscomposedofelementsthat
are located on the righthand side of the periodic table, such as gallium arsenide (GaAs), indium
antimonide (InSb), and silicon carbide (SiC). The number of covalent bonds that is possible for a
particularatomisdeterminedbythenumberofvalenceelectrons.Forvalenceelectrons,anatom
cancovalentlybondwithatmostotheratoms.Forexample,forchlorine,andwhichmeansthatone
Clatomcanbondtoonlyoneotheratom,asinHCl.Similarly,forcarbon,andeachcarbonatomhas
or four electrons to share. Diamond is simply the threedimensional interconnecting structure
whereineachcarbonatomcovalentlybondswithfourothercarbonatoms.

1.2.1.3 MetallicBondingandMetals
Athirdprimarytypeofinteratomicbondingismetallicbondingthatoccursinsolidmetals
andalloys.Arelativelysimplemodelhasbeenproposedthatverynearlyapproximatesthe
above bonding scheme. Metallic materials have one, two, or at most, three valence
electrons.Withthismodel,thesevalenceelectronsarenotboundtoanyparticularatomin
the solid and are more or less free to drift throughout the entire metal. They may be
thought of as belonging to the metal as a whole, or forming a sea of electrons or an
electron cloud. The remaining nonvalence electrons and atomic nuclei form what are
calledioncores,whichpossessanetpositivechargeequalinmagnitudetothetotalvalence
electron charge per atom. Figure 1.11 is a schematic illustration of metallic bonding. The
freeelectronsshieldthepositivelychargedioncoresfrommutuallyrepulsiveelectrostatic
forces, which they would otherwise exert upon one another; consequently the metallic
bondisnondirectionalincharacter.Inaddition,thesefreeelectronsactasagluetohold
theioncorestogether.Bondingenergiesandmeltingtemperaturesforseveralmetalsare
listedinTable1.3.Bondingmaybeweakorstrong;consequentlybondenergiesandmelting
pointsofdifferentmetalsvarygreatly;energiesrangefrom68kJ/mol(0.7eV/atom,melting
point, 39oC) for mercury to 850 kJ/mol (8.8 eV/atom and melting point 3410OC) for
tungsten.

Fig.1.6

In general, fewer valence electrons per atom involved in metallic bonding, the more metallic the
bonding is. The highest degree of metallic bonding is found in alkali metals which have just one
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bondingelectronoutsideanoblegaselectronconfiguration.Asaresult,thebondingenergiesand
meltingpointofalkalimetalsarelow.However,asthenumberofbondingelectronsincreases,the
bonding energy and melting point increase. Further, with the introduction of the 3d electrons in
transitionmetalsoftheperiodfromscandiumtonickel,thebondingenergyandmeltingpointare
raised even much higher. The increased bonding energies and melting points of these transition
elements are attributed to dsp hybridized bondig which involve significant covalent character.
QuantificationofpartialcovalentcharacterinthesemetalshasbeendonebySmithandothersby
assigningcovalentmetallitivitiesbasedontheirmeltingpointin oCascomparedtodiamondwhich
has a melting temperature of 3500oC. It is assumed that diamond has 100% covalent character
amongtheCCbondsandcovalentmetallitivity(CM)ofdiamondisassumedtobe4.TheCMvalues
oftransitionmetalsarescaledaccordinglyaspertheirmeltingtemperature.Forexample,pureiron
has its melting point 1535oC and hence it could be assigned a CM value of
4.0 1.75.
.

Partialcovalentcharacterinironcouldbefurtherdeterminedby,
100 43.7 %.

When3dand4sorbitalsarefilledtheouterelectronsbecomemorelooselyboundandthe
bondingenergiesandmeltingpointsofthemetalsdecreaseagain.Forinstance,zincwith3d104s2
electronconfigurationhasarelativelylowbondingenergyof131KJ/molandmeltingtemperatureof
419oC.

Problem:

1.2.2 SecondaryBonding
In the previous section we showed that primary bonding is largely the manifestation of
interactionofthevalenceelectronsofbondingatoms.Thedrivingforceforprimarybonding
is the energy minimization of the bonding atoms by means of attaining stable electron
configurations of nearest noble gas. On the other hand, the driving force for secondary
bondingistheelectrostaticattractionoftheelectricdipolescontainedintheatomsorthe
molecules.
Bonding energies in secondary bonds are typically of the order of only 10 kJ/mol (0.1
eV/atom) which is way too small than those of primary bonds. Secondary bonding exists between
virtually all atoms or molecules but its presence may be obscured if any of the three primary
bonding types is present. Secondary bonding is evidenced for the inert gases, which have stable
electronstructures,and,inaddition,betweenmoleculesinmolecularstructuresthatarecovalently
bonded. Secondary bonding forces arise from atomic or molecular dipoles. In essence, an electric
dipole exists whenever there is some separation of positive and negative portions of an atom or
molecule.Thebondingresultsfromthecoulombicattractionbetweenthepositiveendofonedipole
and the negative region of an adjacent one as shown in Fig. Dipole interactions occur between
induceddipoles,betweeninduceddipolesandpolarmolecules(whichhavepermanentdipoles),and
betweenpolarmolecules.Hydrogenbonding,aspecialtypeofsecondarybonding,isfoundtoexist
betweensomemoleculesthathavehydrogenasoneoftheconstituents.Ingeneral,therearetwo
main kinds of secondary bonds between atoms/molecules involving electric dipoles: fluctuating
dipolesandpermanentdipoles.CollectivelytheyaresometimesreferredtoasvanderWaalsbonds.

1.2.2.1 FluctuatingDipoles
Veryweaksecondarybondingforcescanarisebetweenatomsofnoblegaselementsthathavefilled
outer valence electron shells. The bonding force arises due to asymmetric electron distribution
aroundthenucleusleadingtotheformationofelectricdipoles.Whiletheoverallspatialdistribution
oftheelectronsissymmetricwithrespecttothepositivelychargednucleus,vibrationalmotioncan
cause instantaneous and shortlived distortions of this electrical symmetry for some of the atoms,

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andresultinsmallelectricdipoles.Thusinaparticularatomtheelectronchargecloudwillchange
withtimecreatingafluctuatingdipole.Fluctuatingdipolesofnearbyatomscanattracteachother,
givingrisetoweakinteratomic,nondirectionalbonds.Liquefactionandsolidificationofnoblegases
atlowtemperatureandhighpressureareattributedtofluctuatingdipolebonds.

Fig.1.7

1.2.2.2 PermanentDipoles
Permanentdipolemomentsexistinsomemoleculesbyvirtueofanasymmetricarrangementof
positivelyandnegativelychargedregions;Inaneffectmoleculesconcentrationsofnegativeand
positivechargesdonotcoincideleadingtoanetdipolemoment.Suchmoleculesaretermedpolar
molecules.Chargepolaritywithinthemoleculeresultsheadtotailelectrostaticattractionof
adjacentdipolesandconsequentbonding.

Fig.1.8

Cl

1.2.3 MixedBonding
Interatomicbondingofatomscaninvolvemorethanonetypeofprimarybondandcanalso
beassociatedwithsecondarybonding.Forprimarybondingtherecanbefollowing
combinationsofmixedbondingtypes:
1.2.3.1 IonicCovalentMixedBonding
Most covalently bonded materials have partial ionic character and viceversa. Partial ionic
character is described in terms of electronegativity scale Greater the difference in
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electronegativity, more ionic the bond is. Pauling proposed the following rule to quantify
partial ionic character in covalently bonded compound, AB where A and B are atoms
formingthecompound.
%

100 %(1.12)

Where, XA and XB are the electronegativities of the atoms A and B, respectively.

Semiconducting materials such as GaAs demonstrates such mixed ioniccovalent mixed
bondingtype.Thedegreeofioniccharacterinthebondingofthesecompoundsincreases
withtheincreaseinthedifferenceofelectronegativitiesoftheconstituentatoms.
1.2.3.2 MetallicCovalentMixedBonding
Mixedmetalliccovalentbondingiscommonlyfoundintransitionmetalswithhighmelting
temperatures and large binding energies. In these metals, hybridized dsp bonding orbitals
renderthecovalentcharacter.Otherexampleofmixedmetalliccovalentbondingisfound
ingroup4Aelements,whereaswemovedowninthecolumnthereisagradualtransition
frompurelycovalentcarbontopartialmetalliccharacterinsiliconandgermanium.
1.2.3.3 MetallicIonicMixedBonding
If there is significant difference in electronegativity in the elements that form an
intermetalliccompound,theremaybeasignificantamountofelectrontransferleadingto
ionic character in the compound. Some intermetallic compounds such as NaZn13
demonstratesmixedmetallicionicbondingcharacteristics.

References:
1. FundamentalsofCeramics,M.W.Barsoum,CRCPress(2002).
2. MaterialsScienceandEngineering,W.F.Smith,J.HashemiandR.Prakash(4thEd.),McGraw
Hill,(2008)
3. MaterialsScienceandEngineering:AnIntroduction,W.D.CallisterJr.,D.G.Rethwisch,John
WileyandSons;8thedition(2009)
4. IntroductiontoCeramics,W.D.Kingery,H.K.Bowen(Author),DonaldR.Uhlmann,Wiley
Interscience;2ndedition(1976)
5. Essentials of Materials Science and Engineering, D. R. Askeland, P. P. Fulay, Cengage
Learning;2nded.(2009)
6. AtomisticPropertiesofSolids,Dinker B. Sirdeshmukh, Lalitha Sirdeshmukh, K.G. Subhadra,
Springer, (2011)

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Roy,Amritendu
IntroductiontoMat.Sc.andEngg.

Fall2016,IITBhubaneswar