Bonding Lect1

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Bonding in Soilds

Bibhas Bhattacharyya
Dept. of Physics, WBSU

● Crystalline solids are formed by periodic repeatition of atoms/


molecules/ ions (revealed by x-ray scattering)

►Why do atoms / molecules / ions bind together?

►There must be some (attractive) interaction (range ~ 1Å)!


Unless there is an interaction free atoms should not care for others.
Interaction is electrostatic!
Gravity is too weak; Nuclear interactions are too short-ranged!
Review: Binding of a diatomic molecule

Atoms cannot penetrate each other: Pauli exclusion!
► V (r )→∞ , as r →0. ( r : interactomic distance.)

For large r, atoms are “free”: V (r )→0.

For finite r there must be an attractive force: V (r ) < 0.
At equilibrium: bond-length r0
V(r) minimum => No force!
|V(r0)| gives the binding energy!
► Similar thing happens for a solid!
Different types of Bonding in Solids

Origin and Nature of attractive interaction are different for different
solids!

Major types of bonding:
1) Van der Waals bonding: cryastals of inert gases (Solid Ne or Ar).
2) Ionic bonding: crystals of alkali halides (NaCl or Kcl).
3) Covalent bonding: crystals of Group 4 elements (C, Ge or Si).
4) Metallic bonding: crystals of metallic elements (Na, Cu or Ag).
5) Hydrogen bonding: ice crystals and certain ferroelectric crystals.
Some Important Definitions

Cohesive Energy:


Lattice Energy:

[See Kittel, 8 th ed., pp. 49]


Crystals of Inert Gas: Van der Waals Bonding

Inert gas atoms have “filled” outer shell:
⇨ sherically symmetric charge distribution ⇨ very stable structure.

Inert gas atoms do not form diatomic molecules!

Solids form at very low temperatures (close packing: fcc structures)!

Melting Point very low: Ne → ~25 K; Ar → ~84K; Kr → ~116K
He does not crystallize! [zero-point K.E. is high due to low mass]

Cohesive energy is low! Ne → ~ 0.02 eV/atom; Kr → ~.12 eV/atom

However, there are temporal fluctuations in electronic charge
density ⇨ temporary dipole moments ⇨ induced dipole moments!
Van der Waals Interaction... contd.

Two atoms interact via induced dipolar interaction ⇨ attraction!

No direct overlap of charge densities is required!

A crude Model: Two oscillating (SHO) linear dipoles interact...


Unperturbed Hamiltonian: ( )

Interaction: , where
Van der Waals Interaction... dipolar attraction

Effective interaction becomes:

To diagonalize introduce normal mode coordinates and momenta
⇨ and


HW 1: check that the total Hamiltonian is now decoupled:

Two oscillators with frequencies: and !


Dipolar Interaction... contd.

New frequencies are:

ω s , ωa =


Zero point energy is lowered! →

Reduction in zero point energy: ⇨ Binding!


1 1

Dipolar Field: ~ 3 ⇨ Induced dipole moment ~ 3
R R
1
⇨ Dipole-dipole interaction energy ( ⃗p . E⃗ ) : ~ 6
R
[Binding stabilizes in a solid due to quenching of fluctuation!]
Van der Waals Bonded Solids

Van der Waals bonding is weak quantum effect:
B

Repulsive part of interactomic potential is best fitted to be ~ 12
R
⇨ Lennard-Jones Potential:

Fitting parameters are [ ; ]

Total potential energy:
● Rpij is the distance between a pair {i, j} of sites.
For fcc lattice z = 12 ⇨

HW 2: Calculate equilibrium bond length R0 : ( dU tot / dR ) R= R = 0
0
Van der Waals Bonded Solids... contd.

For fcc structure : in close agreement with expt.


Departure for lighter atoms: larger zero point K.E. (neglected here)!

HW 3: Estimate cohesive energy U tot ( R=R 0 )
⇨ For fcc:

Error is 4 – 6% in case of heavier atoms;
Larger error for lighter ones due to
quantum (K.E.) corrections.
[see Kittel, 8th ed., chap.3, pp.60] fcc inert gas crystal
Ionic Bonding

Ionic crystals are composed of +ve and -ve ions. Example: NaCl

Periodic array of Na + and Cl− bind electrostatically.

Why do ions form? Na + and Cl− have stable inert gas cofiguration!
Energy considerations: Na + 5.14 eV → Na+ + e− No energy gain!
− −
Cl + e → Cl +3.61 eV

However, electrostatic attraction may further lower the energy!

Equilibrium separation between Na + and Cl− pair: 2.81 Å
⇨ energy gain ~ 5.1 eV; In a crystal there are more no. of bonds...

Energy gain per ion pair: ~7.8 eV! Crystal stabilizes!
Binding by ionic interaction

Electrostatic interaction is long-


ranged!
An ion interact with nearest-
p
neighbours (nn), nnn, nnnn...
This includes both + & - ions
Electrostatic energy of a reference
Lattice i-th atom: e2 (±1)
U i = =− ∑i≠ j
R p ij
R: nn separation; | R⃗ij | = p ij R .
Attractive Potential in Ionic Bonding
(±1)

Define Madelung constant: α = ∑ j ≠i pij
N e2 α

Total Coulombic attractive energy for 2N ions: EC = −
R

Calculation of Madelung Constant– an illustration: 1-d crystal
Start from a reference
-ve ion, and count on
both sides for nn, nnn, ...

⇨ α = 2 ln 2 ≃ 1.3863

⇨ For NaCl: α = 1.7476


● EC is called the Madelung energy.
Total energy: Repulsive counter-part
e2α

Attractive energy per ion pair: −
R
β

Repusive potential between the pair: n
[m need not be 12 as in case of inert gas]
R
β e2 α
● Potential energy per ion pair: U 1 ( R) = n − [Van der Waals potential
R R
∂U 1 ( R) negligible here]

Equilibrium separation: = 0 at R = R 0
∂R
α e 2 n −1 e2 1
⇨ β=
n
R0 ; U N ( R0 ) = −N α
R0 n ( )
1− = N ϵ L ← Lattice energy


How to estimate the exponent n ? Use the compressibility data!

Often people tried a screend Coulomd repulsion: β exp(−R/ ρ) [see Kittel]
Compressibility of Ionic Crystal

Compressibility: K = V 0 ( ∂2 U / ∂ V 2 )V =V 0


For NaCl, no. of Na + - Cl− pair:
4 pairs in a cubic volume of side 2R
3
⇨ Volume per ion pair: V = 2 R 2R
∂U 1 ∂U
⇨ = .
6 R ∂R
2
∂V
∂2 U 1 ∂ 1 . ∂U

∂V
2
= 2
.(
36 R ∂ R R ∂ R
2 )
18 R04
⇨ HW: At equilibrium separation, n = 1 + 2
Ke α

From expt. data: n ~ 8 for NaCl: ϵ L ~ 8.0 eV (expt. ~ 7.9 eV )
Crystal Structure of Ionic Solids

Actual ionic arrangement / crystal structure depends on relative
ionic radii and the inter-ionic distance!

Examples: [see A. K. Raychaudhuri for details]

CsCl structure NaCl structure


Ionic radii: Different Crystal Structures

Ratio of ionic radii and ionic bond determine the structure:

Remember how the extent of packing differs from NaCl to CsCl.

NaCl: fcc space lattice CsCl: sc (primitive cell)

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