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University of Hamburg, Institute of Mineralogy and Petrology

Raman and IR spectroscopy in materials science. Symmetry analysis of normal phonon modes
Boriana Mihailova

Outline

1. The dynamics of atoms in crystals. Phonons 2. Raman and IR spectroscopy :
most commonly used methods to study atomic dynamics

3. Group theory analysis :
phonon modes allowed to be observed in IR and Raman spectra

Atomic dynamics in crystals
Visualization: UNISOFT, Prof. G. Eckold et al., University of Göttingen UNISOFT

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KLiSO4, hexagonal

Crystal normal modes (eigenmodes) Atomic vibrations in crystals = Superposition of normal modes (eigenmodes) e..g. a mode involving mainly S-Ot bond stretching a mode involving SO4 translations and Li motions vs K atoms .

{ui}s ) crystals : N atoms in the primitive unit cell vibrating in the 3D space 3N degrees of freedom finite number of normal states quantization of crystal vibrational energy N atoms × 3 dimensions ↔ 3N phonons phonon ≡ quantum of crystal vibrational energy phonons: quasi-particles (elementary excitations in solids) .integer spin Bose-Einstein statistics: n(ω.T)= 1/[exp(ħω/kBT)-1] (equilibrium population of phonons at temperature T) Harmonic oscillator n=3 n=2 n=1 n=0 ψ ψ2 λ .Phonons Atomic vibrations in a periodic solid standing elastic waves ≡ normal modes (ωS. K ≡ q ∈ RL .En = (n+1/2)ħω. . p = ħK (quasi-momentum).m0 = 0.

q = 1 mi u iα .q = ∑ Dii '.. K({ri})..Phonon frequencies and atom vector displacements a m1 K m2 Atomic bonds ↔ elastic springs Hooke’s low : mx = − Kx ω= K m Equation of motion for a 3D crystal with N atoms in the primitive unit cell : ω wiα . {ri}) phonon ωS.αα ' (q) wi 'α '.. {ui}s carry essential structural information ! .q 2 i 'α ' wiα . q α = 1.2.. N atomic vector displacements dynamical matrix Dss 'αα ' (q) = 1 m s ms ' Φ ss 'αα ' (q) second derivatives of the crystal potential in a matrix form: ω 2 w q = D(q) ⋅ w q (3N×1) (3N×3N) (3N×1) (D(q) − ω δ)⋅ w 2 q =0 phonon ωS. {ui}s ↔ eigenvalues and eigenvectors of D = f (mi.3 i = 1.

out-of-phase phonon dispersion: ωac(q) ≠ ωop(q).Types of phonons diatomic chain Acoustic phonon: u1. ωop > ωac qa qa chain in 1D chain in 3D 3D crystal with N atoms per cell : 3 acoustic and 3N – 3 optical phonons induced dipole moment interact with light 1 Longitudinal: wave polarization (u) || wave propagation (q) Longitudinal 2 Transverse: wave polarization (u) ⊥ wave propagation (q) Transverse LA LO TA TO . u2. in-phase Optical phonon: u1. u2. for q ≈ 0.

phonon interaction): Infrared absorption: ( phonon ( phonon ω photon = EES ) − EGS ) ω. ks ω s ks = ki − K ω s = ωi + Ω anti-Stokes ks = ki + K . ki ω s = ωi − Ω Stokes .Phonon (Raman and IR) spectroscopy electromagnetic wave as a probe radiation (photon – opt. k excited state ground state Raman scattering ≡ inelastic light scattering from optical phonons anti-Stokes Stokes ωι.

[cm-1] = 108 • IR and Raman spectra are different for the same crystal different interaction phenomena different selection rules ! .24 [meV] 10 [cm-1] 0. Raman. 180°-scattering geometry) ki − k s = K π K max << λi (IR.30 [THz] [Å].g.Phonon (Raman and IR) spectroscopy • only optical phonons near the FBZ centre are involved K max = Δk ≈ 2ki (e. vis. UV) ~ 103 – 105 Å ki ~ 10-5 – 10-3 Å ≈ Kmax (a ~ 10 Å) a photon-phonon interaction only for K ≈ 0 E= ħck = ħc(2π/λ) = hc(1/λ) • spectroscopic units: cm-1 10 [cm-1] 1.

! simultaneous IR and Raman activity – only in non-centrosymmetric structures .shell activity ⎛ α xx ⎜ Polarizability tensor: α = ⎜ α xy ⎜α ⎝ xz α (Q) = α 0 + ∑ ∂α Qk + . μ y . “one-directional” Raman activity: induced dipole moment due to deformation of the e. “two-directional” N... μ z ) μ(Q) = μ 0 + ∑ ∂μ Qk + . ∂Qk Qk – configurational coordinate ≠ 0.. IR activity IR: “asymmetrical”.E induced polarization (dipole moment per unit cell) ≠ 0. ∂Qk α xy α xz ⎞ ⎟ α yy α yz ⎟ α yz α zz ⎟ ⎠ P = α.. Raman activity Raman: “symmetrical”.Raman and IR intensities IR activity: induced dipole moment due to the change in the atomic positions activity μ = (μ x .B.

R3m b Pb2 Op P a c b Pb2 Op P Pb1 Ot Pb1 Ot Raman-active Raman-active a c b IR-active a b c Pb2 Op P Pb2 Op P Pb1 Ot Pb1 Ot IR-active Raman-active IR-active .Raman and IR activity in crystals Isolated TO4 group a c Crystal: Pb3(PO4)2.

Methods for normal phonon mode determination Three techniques of selection rule determination at the Brillouin zone centre: • Factor group analysis the effect of each symmetry operation in the factor group on each type of atom in the unit cell • Molecular site group analysis symmetry analysis of the ionic group (molecule) → site symmetry of the central atom + factor group symmetry • Nuclear site group analysis site symmetry analysis is carried out on every atom in the unit cell ☺ set of tables ensuring a great ease in selection rule determination preliminary info required: space group and occupied Wyckoff positions Rousseau. Bauman & Porto.ehu.cryst. Raman Spectrosc. non-resonance interaction processes (one phonon only) (one photon only) (ħωi < EESelectron-EGSelectron) . J.html N.es/rep/sam. (1981) 253-290 Bilbao Server. 10.! Tabulated information for: first-order. http://www. linear-response. SAM.B.

2 . b. c. 3. n. Cn. md. 6 m m. d σg Point groups: Triclinic C1 Ci 1 1 Monoclinic C2 CS C2h C2v D2 D2h 2 m 2/m mm2 222 mmm Trigonal (Rhombohedral) C3 C3i C3v D3d D3 3 3 3m 3m 32 Tetragonal C4 S4 C4h C4v D2d D4 D4h 4 4 4/m 4mm 42m 422 4/mmm Hexagonal C6 C3h C6h C6v D3h D6 D6h 6 6 6/m 6mm 6m2 622 6/mmm Cubic T Th Td O Oh 23 m3 4 3m 432 m3 m Dn: E. 4. mz mv. 4. T: tetrahedral symmetry. 3. nC2 ⊥ to Cn. 6 tn nk a. 2. O: octahedral (cubic) symmetry .Symbols and notations Symmetry element Identity Rotation axes Mirror planes ⊥ to n-fold axis || to n-fold axis bisecting ∠(2.2) Inversion Rotoinversion axes Translation Screw axes Glide planes Schönflies notation E Cn International (Hermann-Mauguin) 1 n = 1. m’ σ σh σv σd I Sn tn k Cn 1 n = 1 .

Symbols and notations normal phonon modes Reminder: ↔ irreducible representations C3 (3) r3 Symmetry element: matrix representation A Character: Tr ( A ) = ∑A i ii σv (m) r1 Point group Symmetry elements characters C3v (3m) reducible 1 3 3 0 1 -1 0 r2 m 1 1 0 1 m: 3: 1: ⎛1 0 0⎞ ⎟ ⎜ ⎜ 0 1 0⎟ ⎜0 0 1⎟ ⎠ ⎝ ⎛ 0 1 0⎞ ⎟ ⎜ ⎜0 0 1⎟ ⎜1 0 0⎟ ⎠ ⎝ ⎛1 0 0⎞ ⎟ ⎜ ⎜ 0 1 0⎟ ⎜0 0 1⎟ ⎠ ⎝ ⎛ ⎜ 0 ⎜1 ⎜0 − 1 ⎜ 2 ⎜ 3 ⎜0 − 2 ⎝ ⎞ ⎟ 0 ⎟ 3⎟ 2 ⎟ 1⎟ − ⎟ 2⎠ irreducible A1 E A1 + E 1 2 3 Mulliken symbols ⎛1 0 0⎞ ⎟ ⎜ ⎜0 0 1⎟ ⎜ 0 1 0⎟ ⎠ ⎝ ⎛1 0 0 ⎞ ⎜ ⎟ ⎜0 1 0 ⎟ ⎜ 0 0 −1⎟ ⎝ ⎠ reducible irreducible (block-diagonal) .

Xu) : symmetric or anti-symmetric to inversion 1 superscripts ’.….2 (X1.….” (X’. B : 1D representations ↔ non-degenerate (single) mode only one set of atom vector displacements (u1.…. u2.Mulliken symbols A. u (Xg. u2. m or Cn 2D system Y X E mode 3D system Y Z X T mode . X2) : symmetric or anti-symmetric to add.uN) for a given wavenumber ω subscripts g.uN) for a given wavenumber ω T (F): 3D representation ↔ triply degenerate mode three sets of atom vector displacements (u1.uN) for a given wavenumber ω A: symmetric with respect to the principle rotation axis n (Cn) B: anti-symmetric with respect to the principle rotation axis n (Cn) E: 2D representation ↔ doubly degenerate mode two sets of atom vector displacements (u1. X”) : symmetric or anti-symmetric to a mirror plane m subscripts 1. u2.

2/3. calcite.1/3)+ (1/3.25682 0 0 0.es/ or google “Bilbao server” or input. then click .2/3)+ Ca: (6b) 0 0 C : (6a) 0 0 O : (18e) 0.25 http://www. R3c (167) D3d6 (0. SAM Working example: CaCO3.25 0.cryst.0)+ (2/3.ehu.0.Bilbao Crystallographic Server.1/3.

SAM Calcite Ca: (6b) 0 0 C : (6a) 0 0 O : (18e) 0.25682 0 0 0.25 .25 0.Bilbao Crystallographic Server.

Bilbao Crystallographic Server. SAM Calcite Point group number of operation of each class symmetry operations selection rules Raman-active αxx = αyy ≠ αzz non-zero components IR-active μz ≠ 0 μx . μ y ≠ 0 αxx = -αyy ≠ αxy αxz≠αyz (xz.yz) + acoustic rotation (inactive) normal modes Ca: (6b) : C : (6a) : O : (18a) : characters A1u + A2u + 2Eu acoustic: A2u+Eu (the heaviest atom) A2g + A2u + Eg + Eu A1g + A1u + 2A2g + 2A2u + 3Eg + 3Eu (N = 6:3 +6:3+18:3 = 10) Total: 10A + 10E = 30 3N = 30 Γopt = A1g(R) + 2A1u(ina) + 3A2g(ina) + 3A2u(IR)+ 4Eg(R) + 5Eu(IR) 5 Raman peaks and 8 IR peaks are expected .

Spectra from 2 5 4 3 1 .

☺ ΓRaman-active = A1g + 4Eg ΓIR-active = 3A2u + 5Eu .Spectra of Calcite from Hamburg.

25 0.Bilbao server. aragonite.68065 Solution: Solution Γopt = 9Ag(R) + 6Au(ina) + 6B1g (R) + 8B1u (IR) + 9B2g (R) + 5B2u (IR) + 6B3g (R) + 8B3u (IR) 30 Raman peaks and 21 IR peaks are expected .25 0.47347 0. SAM Practical exercise: number of expected Raman and IR peaks of aragonite exercise CaCO3.4150 0.09557 0.24046 0.25 0.08726 0.08518 0.76211 0. Pnma (62) D2h16 Ca C O1 O2 : : : : (4c) (4c) (4c) (8d) 0.92224 0.

Spectra of CaCO3 Calcite: ΓRaman-active = A1g + 4Eg Aragonite: ΓRaman-active = 9Ag + 6B1g + 9B2g + 6B3g 22 observed .

25 0 0 0 .255 0.5 B’/B’’: (1a): 0 0 O: (3d): 0.25 0 0.25 0 0 0 0.0)+ A : B’ : B”: O : (8c) : (4a) : (4b) : (24e): 0.Bilbao server.5 0 0 AB’0.B”)O3 Pm3 m (221) O 1 h A: (1b): 0.5 0 0.1/2)+ (1/2.5 0.5B”0. SAM Perovskite-type structure ABO3 double perovskite-type single perovskite-type chemical B-site disorder chemical 1:1 B-site order A(B’.0.1/2.1/2)+ (1/2.5 0.5O3 Fm3 m (225) O 5 h (0.1/2.0.0)+ (0.

SAM A(B’. .Bilbao server. transl.B”)O3 Pm3 m (221) O 1 h A: (1b): T1u B: (1a): T1u O: (3d): 2T1u + T2u Total: 5T = 15 acoustic 3N (5 atoms) Γopt = 3T1u(IR) + T2u(ina) z y x BO6 stretching (3 sets) BO6 bending (3 sets) (3 sets) B-c.

and add.Bilbao server. Eg. T1u Exercise A: B’: B”: O: (8c): (4a): (4b): (24e): T1u acoustic T1u + T2g T1u T1u A1g + Eg + T1g + 2T1u + T2g + T2u Total: 1A+1E+ 9T = 30 3N (N=8:4+4:4+4:4+24:4) Γopt = A1g + Eg + T1g(ina) + 3T1u(IR) + T2u(ina) A1g Eg T2g T2g T1u z y x .5B”0. T2g. SAM AB’0.5O3 Fm3 m (225) O 5 h Exercise: determine the atom vector displacements for A1g.

025 0.595 -0.5 0.0 Ti: (1a): 0.515 0.4853 0.5 tetragonal 14 Amm2 (38) C 2v orthorhombic 5 R3m (160) C 3v rhombohedral P4mm (99) C Ba: (1a): Ti: (1b): O1: (1b): O2: (2c): 0.248 Ba: (1a): 0.0 0.0 .4853 0.0 0.0.0 0.5 0.5 0.0 0.5 0.0 0.489 Ba: (2a): Ti: (2b): O1: (2b): O2: (4c): 0.1/2)+ 0.5 0.Bilbao server.0 0.5 0.1/2.5 0.009 0.264 0. SAM Perovskite-type structure ABO3 : ferroelectric phases BaTiO3 1 Pm3 m (221) O h cubic Ba: (1a): 0.5 0.5 0.4853 O: (1b): 0.0 0.5088 0.0 0.0 Ti: (1b): 0.0185 0.0 0.5 0.0)+ (0.5088 0.5 1 4v (0.5 0 0.595 O: (3c): 0.0 0.5 0.

SAM Perovskite-type structure ABO3 : ferroelectric phases BaTiO3 Ba: Ti: O: Pm3 m T1u T1u T1u T1u T2u Ba: Ti: O1: O2: P4mm A1 + E A1 + E A1 + E A1 + E B1 + E Ba: Ti: O1: O2: Amm2 A1 + B1 + B2 A1 + B1 + B2 A1 + B1 + B2 A1 + B1 + B2 A1 + A2 + B2 R3m Ba: A1 + E Ti: A1 + E O: A1 + E A1 + E A2 + E Polar modes: modes simultaneously Raman and IR active mode polarization along μ (~ u) LO: q || μ TO: q ⊥ μ αxxz. αyyz.Bilbao server. αzzz .

E is always ⊥ to k) αyy αyyn αzz αzzn αyz αyzn Y ( ZZ ) X n=x n = y.0) αxy αxyn αxz αxzn αzy αzyn αzz αzzn n = x.0) X (YY ) X X ( ZZ ) X X (YZ ) X Ei Es Ei Es Ei Es ki ks Y ( XY ) X (ki = ks+q .directions of the propagation of incident (ki) and scattered (ks) light. B. C – directions of the polarization incident (Ei) and scattered (Es) light IRaman ∝ ααβ Y 2 back-scattering geometry Z ks X (qx. z LO TO right-angle geometry Y Z X Y ( XZ ) X Y ( ZY ) X ki (qx. D .y n=z LO+TO TO .Experimental geometry Infrared transmission (only TO are detectible) IIR ∝ μα2 Iinc Y Z X Itrans polarizer Imeas μz or μy Raman scattering Porto’s notation: A(BC)D A.0.qy.

q z ) X ( ZY ) Z X ( ZX ) Z T2(LO+TO) Ei Es q⊥μ T2(TO) μ = (0. E Z (YX ) Z x α yz q || μ T2(LO) μ = (0..0.0) q z ⊥ μ y α xz X Y Z ks Ei Es ki q = (q x . μ z ) q x || μ μ = (μ x .0) .Experimental geometry cubic system e.μ y .0. Td ( 4 3m ) X Y Z ks ki ki = ks + q q = (0.0.0. q z ) Ei Es Ei Es Z (YY ) Z α yy z αxy A1.g.

Experimental geometry non-cubic system e.g. C3v (3m) (hexagonal setting) X Y Z ks ki Ei Es z Z (YY ) Z α yy x α yy μ = (0.0) q = (0.0.0. q z ) μ = (μ x .0) q = (q x .μ z ) A1(TO) X (Y 'Y ' ) X contribution from x α yy z α yy μ = (μ x .μ y .μ z ) .0.0. q z ) ks ki ks ki Ei Es Ei Es z Y ( ZZ )Y α zz q = (0. q y .0.0.0) E(LO) A1(TO) μ = (0.μ z ) q = (0..0.0) μ = (0.0) A1(LO) E(TO) E(TO) Ei Es Z Y X Y’ Y Z X Z (YX ) Z y α xy μ = (0. trigonal.0.

{E(LO). for TO: U) Cubic crystals: LO-TO splitting covalency of atomic bonding crystals ΔωLO-TO: larger in ionic crystals. smaller in covalent crystals Uniaxial crystals: if short-range forces dominate: if long-range forces dominate : A TO LO E TO LO TO A E LO A E Raman shift (cm-1) Raman shift (cm-1) under certain propagation and polarization conditions → quasi-LO and quasi-TO phonons of mixed A-E character .B(TO)}.E(TO)} systems general rule: ω ( LO) > ω (TO) (the potential for LO: U+E.LO-TO splitting More peaks than predicted by GTA may be observed (info is tabulated) Cubic systems: LO-TO splitting of T modes: T(LO) + T(TO) systems Non-cubic systems: {A(LO) .A(TO)}. {B(LO).

O3(8c) Bi12SiO20:X Bi4Ge3O12:Mn 0.899×1018 cm-3 I 4 32 (Td6) Bi(16c).094 undoped Raman shift / cm-1 Raman shift / cm-1 a change in ILO/ITO depending on type and concentration of dopant . O(48e) 0. O1(27f). Si(2a).476 0. O2(8c).LO-TO splitting LO-TO splitting: sensitive to local polarization fields induced by point defects I23 (T03) Bi(24f). Ge(12a).

f(B’/B”-O) and m(B’/B”) intermediate classes of materials: two-mode over x ∈ (0.One-mode / two-mode behaviour in solid solutions different types of atoms in the same crystallogr. e. 1) . xm) and one-mode over x ∈ (xm. position.g. (B’1-xB”x)Oy two-mode behaviour: • two peaks corresponding to “pure” B’-O and B”-O phonon modes • intensity ratio I(B’-O )/I(B”-O ) depends on x covalent character of chemical bonding : short correlation length relatively large difference in f(B’/B”-O) and/or m(B’/B”) one-mode behaviour: • one peak corresponding to the mixed B’-O/B”-O phonon mode • ~ lineal dependence of the peak position ω on dopant concentration x ionic character of chemical bonding : long correlation length similarity in ri(B’/B”).

5(Ta1-xNbx)0.5O3 two-mode behaviour Pb3[(P1-xAsx)O4]2 T > TC ω= f m .One-mode / two-mode behaviour in solid solutions one-mode behaviour PbSc0.

Non-centrosymmetric crystals with compositional disorder LO-TO splitting + one-mode/two-mode behaviour: we may observe four peaks instead of one ! .

Intensity / a. c-pol.4 0.Transformation of polarizability tensors Y Z X ⎛a 0 0⎞ ⎜ ⎟ ⎜0 a 0⎟ ⎜0 0 a⎟ ⎝ ⎠ 0 ⎞ ⎛b 0 ⎜ ⎟ 0 ⎟ ⎜0 b ⎜ 0 0 − 2b ⎟ ⎝ ⎠ ⎛ 3b 0 0⎞ ⎜ ⎟ ⎜ 0 − 3b 0 ⎟ ⎜ ⎟ ⎜ 0 0 0⎟ ⎝ ⎠ rotZ(ϕ=45°) α ’ = UT α U ⎛a 0 0⎞ ⎜ ⎟ ⎜0 a 0⎟ ⎜0 0 a⎟ ⎝ ⎠ 0 ⎞ ⎛b 0 ⎜ ⎟ 0 ⎟ ⎜0 b ⎜ 0 0 − 2b ⎟ ⎝ ⎠ ⎛ ⎜ ⎜ ⎜ ⎜ ⎜ ⎜ ⎜ ⎝ 0 0 d 2 0 0 d 2 d ⎞ ⎟ 2⎟ d ⎟ 2⎟ ⎟ 0 ⎟ ⎟ ⎠ ⎛ ⎜ ⎜ ⎜ ⎜ ⎜ ⎜ ⎜ ⎝ 0 0 d 2 − 0 0 d 2 Y’ Z X’ ⎛ 0 − 3b 0 ⎞ ⎜ ⎟ ⎜ − 3b 0 0⎟ ⎜ ⎟ ⎜ 0 0 0⎟ ⎝ ⎠ d ⎞ ⎟ 2 ⎟ d ⎟ − 2⎟ ⎟ 0 ⎟ ⎟ ⎠ ⎛ 0 d 0⎞ ⎛ 0 0 0 ⎞ ⎛ 0 0 d ⎞ ⎟ ⎜ ⎟ ⎜ ⎟ ⎜ d 0 0⎟ ⎜ 0 0 d ⎟ ⎜ 0 0 0 ⎟ ⎜ ⎜ 0 0 0⎟ ⎜ 0 d 0 ⎟ ⎜ d 0 0 ⎟ ⎠ ⎝ ⎠ ⎝ ⎠ ⎝ 0. A1g(O) + Eg(O) F2g(O) + F2g(Pb) 0.6 0.00 100 200 300 400 500 600 -1 700 800 900 100 200 300 400 500 600 -1 700 800 900 Raman shift / cm Raman shift / cm . p-pol. p-pol.u.u.2 0.0 ⎛d 0 ⎜ ⎜0 −d ⎜0 0 ⎝ 0⎞ ⎟ 0⎟ 0⎟ ⎠ PSTcpp 0 deg.10 I(F2g ) I(Eg ) 0.15 PSTccp 0 deg.8 0.20 1. Intensity / a. 0. PSTdcp 45 deg.05 0. PSTdpp 45 deg.0 0. c-pol.4 1.2 1.

hardly resolved peaks) What should we do before performing a Raman or IR experiment? . time scale ~ 10-12 s) • Experimental difficulties (low-intensity peaks.Conclusions Group theory: predicts the number of expected IR and Raman peaks one needs to know: crystal space symmetry + occupied Wyckoff positions Deviations from the predictions of the group-theory analysis: • ☺ LO-TO splitting if no centre of inversion (info included in the tables) • ☺ one-mode – two-mode behaviour in solid solutions • ☺☺☺ local structural distortions (length scale ~ 2-3 nm.