Bonding Lect1
Bonding Lect1
Bonding Lect1
Bibhas Bhattacharyya
Dept. of Physics, WBSU
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Lattice Energy:
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Unperturbed Hamiltonian: ( )
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Interaction: , where
Van der Waals Interaction... dipolar attraction
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Effective interaction becomes:
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To diagonalize introduce normal mode coordinates and momenta
⇨ and
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HW 1: check that the total Hamiltonian is now decoupled:
ω s , ωa =
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Zero point energy is lowered! →
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Departure for lighter atoms: larger zero point K.E. (neglected here)!
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HW 3: Estimate cohesive energy U tot ( R=R 0 )
⇨ For fcc:
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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
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Ionic crystals are composed of +ve and -ve ions. Example: NaCl
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Periodic array of Na + and Cl− bind electrostatically.
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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
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However, electrostatic attraction may further lower the energy!
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Equilibrium separation between Na + and Cl− pair: 2.81 Å
⇨ energy gain ~ 5.1 eV; In a crystal there are more no. of bonds...
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Energy gain per ion pair: ~7.8 eV! Crystal stabilizes!
Binding by ionic interaction
⇨ α = 2 ln 2 ≃ 1.3863
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How to estimate the exponent n ? Use the compressibility data!
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Often people tried a screend Coulomd repulsion: β exp(−R/ ρ) [see Kittel]
Compressibility of Ionic Crystal
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Compressibility: K = V 0 ( ∂2 U / ∂ V 2 )V =V 0
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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
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From expt. data: n ~ 8 for NaCl: ϵ L ~ 8.0 eV (expt. ~ 7.9 eV )
Crystal Structure of Ionic Solids
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Actual ionic arrangement / crystal structure depends on relative
ionic radii and the inter-ionic distance!
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Examples: [see A. K. Raychaudhuri for details]