Chapter 3.

Crystal Binding
2
 Forces that is involve in bonding

• Attractive forces
• Is necessary for any bonding.

• Repulsive forces
• Required to keep the atoms from
• getting too close to each other

3
INTERATOMIC BONDING
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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Energy level diagram for sodium and chlorine.

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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 HOW TO UNDERSTAND THE INTERATOMIC BINDING GRAPH??

Unhappy
-Unstable
-High Energy
Happy
- Stable Na+ & Cl-
- Low energy

NaCl

Summary
- Binding energy of NaCl = 4.2 eV
- Jarak keseimbangan antara Na+ & Cl- bg membentuk NaCl ialah 0.24 nm 22
Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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 Ionic Covalent Metallic Van der Waals Hydrogen
Energy is released
when atoms form
bonds while energy is
absorbed to break apart
bonds,
- which is why
breaking bonds is
positive and forming
bonds is negative.
- It takes energy and
stress to get
"divorced."
- Atoms are much
happier when they
are "married" and
release energy
because it is easier
and more stable to
be in a relationship.
- The energy change
is negative because
the system is gives
off energy when a 25
bond is formed.
Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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 Ionic Covalent Metallic Van der Waals Hydrogen

Short bonds are

strong - making
Diamond the
hardest natural
substance and
giving it a high
melting point.

Since all the electrons are localised in bonds there is nothing to carry charge through the solid.

Hence, it is a terrible conductor of electricity.

But its very regular lay out makes it transparent.

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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NOW, CAN YOU PLEASE EXPLAIN THE GRAPH OF COVALENT BONDING
OF HYDROGEN?

INTERATOMIC BINDING ENERGY GRAPH HYDROGEN MOLECULE

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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 Ionic Covalent Metallic Van der Waals Hydrogen
Metallic solids have two main examples which are copper and aluminum.

These two metals have a metallic bond, ductile, have low strength and
have very low melting points.

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

Differentiate between the two bonds

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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Ionic Covalent Metallic Van der Waals Hydrogen

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TUGASAN 4
 Repulsive Interaction

Pauli exclusion principle →

(non-electrostatic) effective repulsion
Alternative
repulsive term:
Lennard-Jones potential:
λ e− R / ρ
#% σ &12 % σ &6 $
V = 4ε (* + − * + )
(., R - , R - )/

ε, σ determined from gas phase data

 Equilibrium Lattice Constants
12 6
1 $ & σ ' & σ ' %
Neglecting K.E. → E ! U tot = N (4ε ) ∑ (+ , −+ , ) R = n.n. dist
2 + ,
i ≠ j (- pi j R .
+ pi j R , )
/ - . 0
12 6
# 1 $ # 1 $
For a fcc lattice: α12 = ∑ % && = 12.13188 α6 = ∑ % && = 14.45392
% p
i≠ j' ij (
% p
i≠ j' ij (

α12 = 12.13229 α 6 = 14.45489

For a hcp lattice:

dE 1 $ & σ 12 ' & σ 6 '%

At equilibrium: = 0 ! N (4ε ) ) −12α12 + 13 , + 6 α 6 + 7 , *
dR 2 / -R . - R .0
1/6
→ R0 # 2α $
= % 12 & ! 1.09 for fcc lattices
σ ' α6 (

Experiment (Table 4):

Error due to zero point motion

 Cohesive Energy
1 $ & σ '12 6
&σ ' %
U tot (R ) = N (4ε ) )α12 + , − α 6 + , *
2 )/ - R . - R . *0

1 α 62 α 62
U tot (R 0 )= − N ε = − N (4ε ) ! − N (4ε )(2.15 ) for fcc lattices
2 α12 8α12

For low T, K.E. ≈ zero point motion.

! → p2 !2 1
For a particle bounded within length λ, p" K .E . = " ! "ω
λ 2m 2mλ 2 2

∴ quantum correction is inversely proportional to the atomic mass:

~ 28, 10, 6, & 4% for Ne, Ar, Kr, Xe.
 Ionic Crystals

ions: closed outermost shells ~ Cohesive/Binding energy =

spherical charge distribution 7.9+3.61−5.14 = 6.4 eV
 Electrostatic (Madelung) Energy

Interactions involving ith ion: U i = ∑U i j

j≠ i

$ −R/ ρ q2
%λ e −
R
n.n.
%
Ui j = & 2
% ± q
otherwise
%' pi j R

U tot = NU i
% −R/ ρ α q2 &
For N pairs of ions: = N ' zλ e − ( z ﹦number of n.n.
) R *
ρ ~ .1 R0
α =∑
(± )
pi j
﹦Madelung constant
j≠i

dU tot % zλ − R / ρ α q 2 &
At equilibrium: = 0 = N '− e + 2 ( − R0 / ρ ρ α q2
→ 2
R e =
dR ) ρ R * 0
zλ

Nα q 2 # ρ $ Nα q 2
U tot 0 =− &&1 − '' Madelung Energy = −
R0 ( R0 ) R0
 Evaluation of Madelung Constant
App. B: Ewald’s method
α =∑
(± )
i fixed
j≠i pi j

" 1 1 1 #
α = 2 %1 − + − + ! & = 2 ln 2
' 2 3 4 (

KCl
Kcal/mol = 0.0434 eV/molecule Prob 3.6
 Covalent Crystals
H2

• Electron pair localized midway of bond.

• Tetrahedral: diamond, zinc-blende structures.
• Low filling: 0.34 vs 0.74 for closed-packed.

Pauli exclusion →
exchange interaction
Ar : Filled outermost shell → van der Waal interaction (3.76A)
Cl2 : Unfilled outermost shell → covalent bond (2A)

s2 p2 → s p3 → tetrahedral bonds
 Metals

Metallic bonding:
• Non-directional, long-ranged.
• Strength: vdW < metallic < ionic < covalent
• Structure: closed packed (fcc, hcp, bcc)
• Transition metals: extra binding of d-electrons.
 Hydrogen Bonds

• Energy ~ 0.1 eV
• Largely ionic ( between most electronegative atoms like O & N ).
• Responsible (together with the dipoles) for characteristics of H2O.
• Important in ferroelectric crystals & DNA.
 Atomic Radii

Standard ionic radii

~ cubic (N=6)
Na+ = 0.97A
F− = 1.36A
NaF = 2.33A
obs = 2.32A

Bond lengths:
F2 = 1.417A
Na –Na = 3.716A
→ NaF = 2.57A

Tetrahedral:
C = 0.77A
Si = 1.17A
SiC = 1.94A
Obs: 1.89A

Ref: CRC Handbook of Chemistry & Physics

 Ionic Crystal Radii

E.g. BaTiO3 : a = 4.004A

Ba++ – O– – : D12 = 1.35 + 1.40 + 0.19 = 2.94A → a = 4.16A
Ti++++ – O – – : D6 = 0.68 + 1.40 = 2.08A → a = 4.16A
Bonding has some covalent character.
 Analysis of Elastic Strains
Ref: [Link], [Link], “Theory of Elasticity”, Pergamon Press (59/86)

Continuum approximation: good for λ > 30A.

Description of deformation (Cartesian coordinates): Displacement vector field u(r).

Material point r = xi → r! = r + u (r ) = xi! = xi + ui

Nearby point r + dr = xi + dxi → r! + dr! = r + dr + u (r + dr ) = r + dr + u (r ) + (dr ⋅∇ )u (r ) + !

∂ui
dr! = dr + (dr ⋅∇ )u (r ) + ! dxi" = dxi + dx j +!
∂xj
2 2 2
dl !2 = (dr! ) ! (dr + (dr ⋅∇ )u (r )) = (dr ) + 2dr ⋅ #%(dr ⋅∇ )u (r )$& + #%(dr ⋅∇ )u (r )$& ⋅ #%(dr ⋅∇ )u (r )$&
∂ui ∂u ∂u
= dl 2 + 2dxi dx j + dxi k dx j k
∂xj ∂ xi ∂xj
! ∂ u ∂ u j ∂ uk ∂ uk "
dl $2 − dl 2 = & i + + '' dxi dx j = 2u!i j dxi dx j
& ∂x
( j ∂ xi ∂ xi ∂ x j )
1 ! ∂ui ∂u j ∂uk ∂uk " 1 ! ∂ui ∂u j "
ui j = $
! + + % = strain tensor ui j = $ + %% = linear strain tensor
2 $& ∂ x j ∂ xi ∂ xi ∂ x j %' 2 $& ∂ x j ∂ xi '
 Dilation
uik is symmetric → diagonalizable → ∃ principal axes such that

( ) ( ) ( )
dl "2 = (δ i j + 2u!i j )dxi dx j = 1 + 2u (1) dy12 + 1 + 2u (2) dy22 + 1 + 2u (3) dy32

→ dyi! ! ( i
) ( ()
1 + 2u ( ) dyi ! 1 + u dyi
i
) (no summation over i )

! i "
∴ (
(i )
)
dV ! = ∏ dyi! ! ∏ 1 + u dyi ! #1 + ∑ u ( ) $ dV = (1 + uii )dV
i i % i &

dV ! − dV
Fractional volume change = = uii = Trace of uik
dV
 Stress
Total force acting on a volume element inside solid =
V
∫ f dV f = force density

Newton’s 3rd law → internal forces cancel each other → only forces on surface contribute

∂σ i k
This is guaranteed if fi =
∂ xk
so that
V
∫f i dV = !∫ σ i k dS k
S
σ = stress tensor

σik = ith component of force acting on the surface element normal to the xk axis.

" ∂σ i j ∂σ k j #
Moment on volume element = M ik = ∫ ( fi xk − f k xi )dV = ∫ & x − x dV
& ∂ x k ∂ x i ''
( j j )
∂ " ∂ xk ∂ xi #
=∫
∂xj
(σ i j xk − σ k j xi )dV − ∫ && σ i j ∂ x − σ k j ∂ x '' dV
( j j )

= !∫ (σ i j xk − σ k j xi )dS j − ∫ (σ i k − σ k i )dV

Only forces on surface contribute → σ ik = σ ki (σ is symmetric)

 Elastic Compliance & Stiffness Constants
σ and u are symmetric → they have at most 6 independent components

Compact index notations (i , j) → α :

(1,1) → 1, (2,2) → 2, (3,3) → 3, (1,2) = (2,1) → 4, (2,3) = (3,2) → 5, (3,1) = (1,3) → 6

1 1 i , j , k, l = 1,2,3
Elastic energy density: U = Ci j k l ui j uk l = Cα β uα uβ
2 2 α , β = 1,2,…,6

" uii " 1, 2,3 21

where uα = # for α = # Ci j k l = C j i k l = Ci j l k = C j il k
u
$ ij + u ji $ 4,5, 6 = Ck l i j = Cl k i j = Ck l j i = Cl k j i

Ci j k l = Cαβ = elastic stiffness constants = elastic modulus tensor

∂U 1 uik & uki treated as

Stress: σmn = = Ci j k l (δ mi δ n j uk l + ui j δ m k δ nl )
∂ um n 2 independent
1
=
2
(Cmnk l uk l + Ci j mn ui j ) = Cm n k l uk l

∂U uα = Sαβ σ β
σα = = σ i j = Cα β uβ
∂uα S α β = elastic compliance constants
 Elastic Stiffness Constants for Cubic Crystals
Invariance under reflections xi → –xi ⇒ C with odd numbers of like indices vanishes

Invariance under C3 , i.e.,

x→ y→z→x −x → z → y → −x
x → z → −y → x −x → y → z → −x

⇒ All C i j k l = 0 except for (summation notation suspended):

Ciiii = C1111 Cii k k = C1122 Ci k i k = C1212

1
U = C1111 (u112 + u22
2 2
+ u33 )+ C1122 (u11u22 + u22u33 + u33u11 ) + 2C1212 (u122 + u23
2 2
+ u31 )
2
1 1
= C11 (u12 + u22 + u32 )+ C12 (u1u2 + u2u3 + u3u1 ) + C44 (u42 + u52 + u62 )
2 2
" σ 1 # " C11 C12 C12 0 0 0 # " u1 #
$ % $ %$ %
$ σ 2 % $ C12 C11 C12 0 0 0 % $ u2 %
$ σ 3 % $ C12 C12 C11 0 0 0 % $ u3 %
$ %=$ %$ %
$σ 4 % $ 0 0 0 C44 0 0 % $ u4 %
$σ5 % $ 0 0 0 0 C44 0 % $ u5 %
$$ %% $$ %$ %
&σ 6 ' & 0 0 0 0 0 C44 %' $& u6 %'
 −1
" C11 C12 C12 0 0 0 # " S11 S12 S12 0 0 0 #
$ % $ %
$ C12 C11 C12 0 0 0 % $ S12 S11 S12 0 0 0 %
$ C12 C12 C11 0 0 0 % $ S12 S12 S11 0 0 0 %
$ % =$ %
$ 0 0 0 C44 0 0 % $ 0 0 0 S 44 0 0 %
$ 0 0 0 0 C44 0 % $ 0 0 0 0 S 44 0 %
$$ %% $$ %%
& 0 0 0 0 0 C44 ' & 0 0 0 0 0 S 44 '

C11 + C12 C12 1

where S11 = S12 = − S 44 =
(C11 + 2C12 )(C11 − C12 ) (C11 + 2C12 )(C11 − C12 ) C44

∴ −1
(S11 − S12 ) = C11 − C12 (S11 + 2S12 )
−1
= C11 + 2C12
 Bulk Modulus & Compressibility
1 1
U = C11 (u12 + u22 + u32 )+ C12 (u1u2 + u2u3 + u3u1 ) + C44 (u42 + u52 + u62 )
2 2
δ
Uniform dilation: u1 = u2 = u3 = u4 = u5 = u6 = 0
3
δ = Tr uik = fractional volume change

1 1
U= (C11 + 2C12 )δ 2 ≡ Bδ2 B = Bulk modulus
6 2

1 1 ∂V
B= (C11 + 2C12 ) = 1/κ κ = compressibility =−
3 V ∂p

See table 3 for values of B & κ .

 Elastic Waves in Cubic Crystals
∂ 2 ui ∂σ i k
Newton’s 2nd law: ρ 2 = don’t confuse ui with uα
∂t ∂ xk

∂ 2 ui ∂u jl 1 ! ∂ 2 ul ∂2 u j " ∂ 2 ul
σ i k = Ci k j l u j l → ρ 2 = Ci k j l = Ci k j l $ + %% = Ci k j l
∂t ∂ xk 2 $ ∂ x ∂x ∂ x ∂x ∂ xk ∂x j
& k j k l '

∂ 2 u1 ∂ 2 u1 ∂ 2 u2 ∂ 2 u3 ∂ 2 u2 ∂ 2 u1 ∂ 2 u3 ∂ 2 u1
ρ 2 = C1111 2 + C1122 + C1133 + C1212 + C1221 2 + C1313 + C1331 2
∂t ∂ x1 ∂ x1∂x2 ∂ x1∂x3 ∂ x2 ∂x1 ∂ x2 ∂ x3∂x1 ∂ x3

∂ 2 u1 ! ∂ 2 u2 ∂ 2 u3 " ! ∂ 2 u2 ∂ 2 u1 ∂ 2 u3 ∂ 2 u1 "
= C1111 2 + C1122 $ + % + C1212 $ + 2 + + 2 %
∂ x1 ∂ x
& 1 2 ∂x ∂ x1 ∂x3 ' ∂ x
& 2 1 ∂x ∂ x2 ∂ x3 ∂x1 ∂ x3 '

∂ 2 u1 ∂ 2 u1 " ∂ 2 u2 ∂ 2 u3 # " ∂ 2 u1 ∂ 2 u1 #
∴ ρ 2 = C11 2 + (C12 + C44 )% + & + C44 % 2 + 2 &
∂t ∂ x1 ' ∂ x1∂x2 ∂ x1∂x3 ( ' ∂ x2 ∂ x3 (

Similarly ∂ 2 u2 ∂ 2 u2 " ∂ 2 u3 ∂ 2 u1 # " ∂ 2 u2 ∂ 2 u2 #

ρ 2
= C11 2
+ (C12 + C44 )% + & + C44 % 2 + 2 &
∂t ∂ x2 ∂ x
' 2 3 ∂x ∂ x2 ∂x1 ( ∂
' 1 x ∂ x3 (

∂ 2 u3 ∂ 2 u3 " ∂ 2 u2 ∂ 2 u1 # " ∂ 2 u3 ∂ 2 u3 #
ρ = C11 + (C12 + C44 )% + & + C44 % 2 + &
∂t 2 ∂ x32 ∂ x
' 3 2 ∂x ∂ x3 ∂x1 ( ' ∂ x2 ∂ x12 (
 Dispersion Equation
∂ 2 ui ∂ 2 ul
ρ 2 = Ci k j l
∂t ∂ xk ∂x j

ui = u0 i ei ( k ⋅r − ω t ) → ω 2 ρ u0i = Ci k j l kk k j u0l

(ω ρ δ
2
il − Ci k j l kk k j )u 0l =0

ω 2 ρ δ i l − Ci k j l kk k j =0 dispersion equation

ω 2 ρ I − C (k ) = 0 Ci j (k ) = Ci mn j km kn
 Waves in the [100] direction
ω 2 ρ I − C (k ) = 0 Ci j (k ) = Ci mn j km kn

k = k (1, 0, 0 ) → Ci j (k ) = Ci11 j k 2

! C1111 0 0 " ! C11 0 0 "

# $ # $
C (k ) = k 2 # 0 C2112 0 $ = k 2 # 0 C44 0 $
# 0 0 C3113 $& # 0 0 C44 $&
% %

C11
ωL = k u 0 = (1, 0, 0 ) Longitudinal
ρ

C44 u 0 = (0,1, 0 )
ωT = k Transverse, degenerate
ρ
u 0 = (0, 0,1)
 Waves in the [110] direction
ω 2 ρ I − C (k ) = 0 Ci j (k ) = Ci mn j km kn

k k2
k= (1,1, 0 ) → Ci j (k ) = (Ci11 j + Ci12 j + Ci 21 j + Ci 22 j )
2 2

! C1111 + C1221 C1122 + C1212

2
0 " 2
! C11 + C44 C12 + C44 0 "
k # $ k # $
C (k ) = # C2121 + C2211 C2112 + C2222 0 $ = # C12 + C44 C11 + C44 0 $
2 # 2
% 0 0 C3113 + C3223 $& #
% 0 0 2C44 $&

1
ωL = (C11 + C12 + 2C44 ) k u 0 = (1,1, 0 ) Lonitudinal
2ρ

1
ωT1 = (C11 − C12 ) k u 0 = (1, −1, 0 ) Transverse
2ρ

C44
ωT 2 = k u 0 = (0, 0,1) Transverse
ρ
Prob 3.10