CRYSTALLOGRAPHIC POINT AND SPACE GROUPS. Andy Elvin June 10, 2013

Transcription

1 CRYSTALLOGRAPHIC POINT AND SPACE GROUPS Andy Elvin June 10, 2013

2 Contents Point and Space Groups Wallpaper Groups X-Ray Diffraction Electron Wavefunction Neumann s Principle Magnetic Point Groups

3 Point Groups Subgroups of O(3) 32 Crystallographic Point Groups E, i, C n, σ h, σ v, σ d, S n relevant point groups will be referred to as group P

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5 D 3 symmetries reflection axes C 3 symmetries no reflection axes

6 Cube and Octahedron are dual Symmetries under O h

7 Space Groups Subgroups of E(3) Point Group + Translation { R 0 }{ E t }a = { R t }a = Ra + t 230 Space Groups 73 symmorphic space groups relevant space groups will be referred to as group S

8 Bravais Lattices 14 Lattice Types Defines translations of space group t=n 1 a 1 +n 2 a 2 +n 3 a 3

9 Point Group is C 3 Left: Space Group is P3 2 Right: Space Group is P3 1 Molecule is Chiral

10 Wallpaper Groups Wallpaper Groups Frieze Groups Spherical and Hyperbolic Symmetry Groups

11 The 17 Wallpaper Groups

12 p1 p2

13 p4g p6m

14 Reciprocal Lattice b 1 = (a 2 a 3 )(a 1 [a 2 a 3 ]) -1 cyclically permute indices Fourier Transformed spatial functions Momentum Space k vector

15 X-Ray Diffraction Bragg s Law/Bragg Scattering nλ = 2dsin(θ) X-ray diffraction patterns Fourier Transform

16 Bragg Scattering X-ray plane waves with propagation vector k electron number density n(r) n(r + t) = n(r) translation in reciprocal lattice space: g

17 n(r) = g n g exp[ig r] n(r + t) = g n g exp[ig (r + t)] n(r + t) = g n g exp[ig r] exp[ig t] = n(r) n(r) = g n g exp[ig r] exp[ig t] = g n g exp[ig r] exp[ig t] = 1 => g t = 2πn and finally n(r) = g n g exp[ig r] = n(r + t) for all t S

18 scattering amplitude of incident plane waves, F( k) is given by F( k) = n(r)exp[ir (k - k )]dr and k k - k where k is the direction of propagation of the scattered wave and the integral is taken over all lattice sites and noting that n(r) = g n g exp[ig r], F( k) = g n g exp[ir (g - k)]dr which allows us to conclude that the scattering amplitude is at a maximum when g = k and using the definition of k k = k + g

19 then the elastic scattering of the x-rays implies (k + g) 2 = k 2 = k 2 completing the square yields the two bragg conditions: g 2 + 2(k g) = 0 2(k g) = g 2 after noting that if g is a reciprocal lattice basis vector, so is -g k g = k g cos(ß) ß = θ - π/2 => k g = k g sin(θ), now 2 k sin(θ) = g 2 t sin(θ) = g t / k after noting t = d and k = 2π/λ then g t / k = nλ so finally 2dsin(θ) = nλ

20 X-ray diffraction pattern for NaCl Structure of NaCl

21 Electron Wavefunctions Bloch s Theorem Probability Density Energy invariance Degeneracy of electron energy levels

22 Bloch s Theorem s S, then s(exp[ik r]) exp[isk r] and sf(r) = f(s -1 r) implies s(exp[ik r]) = exp[ik s -1 r] now considering the crystal system described by the space group S, then the potential has periodicity defined by t such that V(r) = V(r + t) Bloch s Theorem States: Ψ k (r) = u k (r)exp[ik r] where u k (r) = u k (r + t)

23 Consider the electrons in the crystal defined by S HΨ = EΨ [H - E]u k (r)exp[ik r] = 0 [H - E]u k (r) = 0 u k (r) is then a solution of Schrodinger s equation for the crystal Probability density Ψ k (r + t) 2 = u k (r + t) 2 exp[i(k r) - i(k r)] = u k (r + t) 2 Ψ k (r + t) = u k (r + t) = u k (r) = Ψ k (r) Energy Ψ k (r + t) = exp[ik t + ik r]u k (r + t) = exp[ik t]ψ k (r) H(Ψ k (r + t)) = H(exp[ik t])ψ k (r) = E(exp[ik t])ψ k (r) E(k) = E(exp[ik t]) = E(exp[i(k + g) t]) = E(k + g)

24 Degeneracy O E 8C 3 3C 2 6C 2 6C 4 Γ Γ Γ Γ Γ O E 8C 3 3C 2 6C 2 6C 4 D D D D D Character Table of the Irreducible Representations D 0 = Γ 1 D 1 = Γ 4 Character Table of the Reducible Representations, D L, corresponding to the spherical harmonics, Y L M D 2 = Γ 3 + Γ 5 D 3 = Γ 2 + Γ 4 + Γ 5 D 4 = Γ 1 + Γ 3 + Γ 4 + Γ 5

25 Neumann s Principle Any physical property of a crystal possesses the symmetry of its point group, P Tensors representing a property are invariant under P Susceptibility, Stress, Polarizability, Inertial, etc...

26 Polarizability Tensor P = C 2h = {E, C 2, i, σ h } T ij = T ji E C 2 i σ h x 2 x 2 x 2 x 2 x 2 y 2 y 2 y 2 y 2 y 2 z 2 z 2 z 2 z 2 z 2 xy xy xy xy xy xz xz -xz xz xz C 2 operation implies T xy = -T xy = 0 T yz = -T yz = 0 This leaves the polarizability tensor with at most four components yz yz -yz yz yz

27 Magnetic Point Groups Magnetic Crystals display different symmetries M is the antisymmetry operator ( black and white, time-reversal, current-reversal ) P = N (P - N) N is an invariant subgroup of P P = N M(P - N) P is the Magnetic Point Group ( black and white point group ) There are 58 Magnetic Point Groups

28 References Michael Tinkham. Group Theory and Quantum Mechanics. Dover Publications, Richard L. Liboff. Primer for Point and Space Groups. Springer, 2004 Bradley and Cracknell. The Mathematical Theory of Symmetry in Solids. Oxford, Burns and Glazer. Space Groups for Solid State Scientists. Academic Press, 1990 Bhagavantarn and Venkatarayudu. Theory of Groups and its Application to Physical Problems. Academic Press, 1969.