Modern Polymer Spect..

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3.5 TOIIYW~ Laiyer Molertiles: Fvoiii Oligomevs to Polimers 103 - Figure 3-2. Dispersion curves \./a, for single chain helical (z = IS, t = 7) polytetrafluoroethylene. 0' 60' 120" lBi plot of v(q) becomes usable while v(k) becomes unreadable (117 frequency phonon branches in k space) (Figure 3-2) [54]. Dealing with 1D chains iii vuczio carries an important consequence on the shape of the dispersion curves if compared with the same systems considered as 3D lattices. From lattice dynamics in 3D it is known that if q is the number of atoms in the crystallographic repeat unit the dispersion relation provides 3q phonon branches. three of which are labeled as 'acoustical' and 3q - 3 as 'optical' branches. The former three have zero frequencies at the so-called r symmetry point in k space (i.e., with k, = k, = k, = 0; see Figure 3-3) and correspond to the three nongenuine vibrations with zero frequencies which describe the three rigid translations of the whole lattice along the three Cartesian coordinates [49. 551. The 3q - 3 optical branches may interact with the electromagnetic waves according to specific selection rules and provide the system with particular optical properties (absorption and/ or Raman scattering), as discussed below. In ID systems iii u~~cuo the rigid rotation of the whole chain about its axis is not hindered. It follows that an additional zero eigenvalue is expected from Eq. (3.43) when applied to 1D systems at k = 0. The lack of intermolecular forces for the polymer chain in uact[o carries an important consequence on the shape of the two acoustic branches near k = 0. While the three acoustic branches for 3D crystals have a discontinuity at k = 0, for ID crystals two of the acoustical branches may approach ~(0) almost asymptotically [56]. It follows that the dynamics of 1D systems based on the model of an isolated chain at small k values and at very low frequencies is totally wrong and cannot be used for the interpretation of related physical properties of real systems (neutron-scattering experiments, thermodynamic properties, Debye Waller factors, mean square amplitudes, and other physical properties where thermal population is involved which is strongly affected by lowenergy vibrations). For the benefit of the discussion which follows we give here a calculated schematic example of the procedures followed in setting up the matrices F~(rp) and
104 3 ViLmrtional <strong>Spect</strong>ra as u Probe oj'StrLrctzrra1 Order cm 12oc 1100 1000 900 800 700 600 500 400 300 200 100 " n 0 I Figure 3-3. Dispersion curves of crystalhe orthorhoiiibic polyethylene with two molecules per unit cell (from [49]). Comparison with Figure 3-1 shows the splitting of the frequency branches and the shape of the acoustical branches at q~ - 0 (see text). Attention should be paid to the fact that the frequencies and the shape of the dispersion curves shown in Figure 3-1 and in this figure may differ because they have been calculated with two different force fields.
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Modern Polymer Spectroscopy Edited
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Modern Polymer Spectroscopy Edited
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Preface For unfortunate reasons the
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However, theory and calculations yi
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Contents 1 Two-Dimensional Infrared
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Con ten t~ xi Index 5.2 Force Field
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Contributors M. Del Zoppo Dipartime
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1 Two-Dimensional Infrared (2D IR)
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1.2 Brick~qrorrnrl 3 . Figure 1-3.
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1.0 , Figure 1-6. The in-phtrse and
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1.2 Bcrckgroinizd 7 where AA (i~) i
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1.2 Background 9 1.2.5 Two-Dimensio
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1.3 Bnsic Properties of 20 IR Corre
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2D IR spectrometer coupled with a d
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1.5 Applirtrtions 15 Unlike a dispe
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\ '\ Melliyleiie 1'7- -3000 Posiliv
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11 Amorphous Crystalline ,...." I F
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1.5 Applications 21 / I 1430 Figure
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1.5 Appliccitioiis 23 Methylene Fig
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1.5 Ajqdicrrtions 25 3024 Figure 1-
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1.5 Applicutions 27 Furthermore. th
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1.7 Coizclirsions 29 derived in a s
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1.9 References 31 [9] Colthup, N. B
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2 Segmental Mobility of Liquid Crys
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SRMPLE/DETECTOR e3 ‘retardation
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2.4 Srvuc me-Dependenr Alignment 37
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2.5 Electric Field-Innductid Orirnt
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2.5 Electric Field-nclticetl Orient
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a -@ COWER SRHPLE ._ 2.5 Elec tric
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2.5 Electric Field-Itzduced Orienta
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2.5 Electric Field-IwrElrced Orient
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2.5 Electric Field-Im/irced Orientu
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2.5 Electric Field-Induced Orientli
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Page 70 and 71: 2.5 Electric Field-Induced Orienfat
Page 72 and 73: 2.5 Elrc tric Field-Iiidircwl Orim
Page 74 and 75: 2500 2008 I s00 WRVtNdMRtR CM-I Fig
Page 76 and 77: -3.6 Aligmient OJ' Side- Clinin Liy
Page 78 and 79: ~ polyester 2.6 Alignnient qf Side-
Page 80 and 81: I." 0.9 0.8 Figure 2-34. FTlR 0.7 p
Page 82 and 83: induced alignment of the investigat
Page 84 and 85: 2.7 Orientation oj Liquid Ci:i,stal
Page 86 and 87: 2.7 Orieritation of Liquid Ciysttrl
Page 88 and 89: 0 8 18 16 1 a W u z a m a 0 Ln m Q
Page 90 and 91: 2.7 Orientation oj Liquid Crystals
Page 92 and 93: 2.7 Orientation of Liquid Crjvtals
Page 94 and 95: 2.7 Orientatioiz of Liquid Crystals
Page 96 and 97: 2.8 Conclusions 81 strain. As A0 is
Page 98 and 99: 3. I0 Refcreiice.r 83 [I 71 Hoffina
Page 100 and 101: 2.10 References 85 [92] Wiesner, U.
Page 102 and 103: t Order/Disorder in Chain Molecules
Page 104 and 105: onds which hold atoms together thro
Page 106 and 107: 3.2 The Dyriamical Case qf Simll ar
Page 108 and 109: 3.2 The Dyrinniical Case of Sinnll
Page 110 and 111: 3.4 S11or.f- and Loizg-Rcrizye Vibr
Page 112 and 113: 3.4 Slzort- and Loiig-Range Vibrati
Page 114 and 115: eyularity), e.g., 2. During the pol
Page 116 and 117: 3.5 Towards Lnrger Molecules: From
Page 120 and 121: 3.5 Towmu" Larger Molecules: F~om O
Page 122 and 123: 1700 - CIO --- ca c 22 _- c 12 l l
Page 124 and 125: 3.6 From Dynamics to Vibrational Sp
Page 126 and 127: 3.6 Froin Dynaiiiics to T’ihratio
Page 128 and 129: 3.7 The Case of Isotactic Polypropy
Page 130 and 131: 3.7 The Cuse of Isotactic Polypvop.
Page 132 and 133: 3.8 Density of Vibrational States a
Page 134 and 135: 3.8 Dtvz.sit,v of L’ihrntioizal S
Page 136 and 137: 3.8 Driisity of Vibratioiid StLitrs
Page 138 and 139: 3 9 Mouiiiq ToIvmds Rerrlitv: From
Page 140 and 141: 3.9 Moving Towards Reality: From Or
Page 142 and 143: 3.9 Moving Towards Reality: Froin O
Page 144 and 145: 3.10 Wlmt Do We Learn from Cnlcailc
Page 146 and 147: + 3.11 A Very Siriiple Ccrse: Latti
Page 148 and 149: 3 I1 A Yey) Siiiiple Case: LLittice
Page 150 and 151: 3.11 A Vq> Siiiiplc Crrw: Luttice D
Page 152 and 153: Figure 3-22. Sample eigenvectors in
Page 154 and 155: 3.12 CIS-trans Opening @the Double
Page 156 and 157: 3.13 Defect Modes cis Structtrr.al
Page 158 and 159: 3.13 Defect Mo&s cis Structurcil Pr
Page 160 and 161: 0 3.14 Case Studies N 0 d - Y N o m
Page 162 and 163: 3.14 Case Studies 147 OC 60 58 57.
Page 164 and 165: 3.14 Case Studies 149 GI A V E N U
Page 166 and 167: 3.14 Case Studies 15 1 correspond t
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3.14 Case Studies 153 (I10 + 200) +
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3.14 Case Studies 155 1500 1480 146
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3.14 Case Studies 157 the molecular
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17E (ir 1, R): (iii) z = 4, t = 1,
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3.16 Stnictural Znlioi~zogeneity an
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3.1 7 Fermi Resonancrs 163 stants.
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3.1 7 Femi Resorinnces 165 2 L 1 29
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lowing. The CHl-bending mode 6 [cer
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3.17 Ferini Re.sonrriire.s 169 a Fi
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3. I7 Fernii Resoiiances 17 1 terin
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3.18 Band Broadening and Confonnati
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3.18 Bmd Brourleiziriy md Cmforrnat
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3.18 Band Bvoaderiing arid Conjonna
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3.18 Band Broadening and Confornmti
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3.19 A Worked E.utinple 181 pre-mel
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3.19 A Wovh-ecl E.uanzple 183
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3.19 A Worked Example 185 19 5°C 2
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3.19 A Workrd Example 187 Figure 3-
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3.19 A Worked E.rcnniplr 189 LAM I
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3.19 A Worked E.xuniple 191 Figure
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3.19 A Worked E.vnn~yle 193 Figure
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3.19 A Worked E.vnrqde 195 009.1 00
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3.19 A Worked Example 197 existence
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3.1 9 A Worked Example 199 The soli
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3.20 References 201 very important,
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3.20 References 203 [41] M. Gussoni
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3.20 Refeeveiicrs 205 [I 171 P. Jon
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4 Vibrational Spectroscopy of Intac
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4.3 Georrietvy oj Intuct Po1vniev.r
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1'45 4.4 Geometric Chunges I?zditce
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4.4 Geometric Chmges Iiid~lrcecl bj
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4 5 Mer1iodolog.v of Raiii~11 Studi
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4.7 Poly(p-pheiq.lene) 217 with an
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4.7 Pol)~(p-pheiz~~lene) 219 ENERGY
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is worthwhile pointing out that the
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~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 801 Table 4-3
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4.7 Poly(y-phenylene) 225 Figure 4-
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Table 4-4. Observed Raman frequenci
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4.8 Other Polwieys 229 Table 4-5. T
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under various models. According to
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4. I0 Mechnriism oj Charge. Transpo
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4.12 Reftrences 235 [ 131 Kuzmany,
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4.12 References 237 [98j Matsunuma,
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5 Vibrational Spectroscopy of Polyp
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5.2 FOYCC Fields 241 such calculati
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5.2 Force Fields 243 accounts for o
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5.2 Force Fields 245 centers of the
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5.2 Force Fields 247 ture with conf
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5.3 Amide Modes 249 to the nh initi
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5.3 Ainide Modes 251 Table 5-1. Ami
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Table 5-2. Some amide modes of four
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5.3 Amidc Modes 255 Figure 5-1. Opt
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5.4 Polypeptides 257 nonhydrogen-bo
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5.4 Polvpeptida 259 Figure 5-2. Ant
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I 5.4 Polypeptides 261 )I .- + $ 80
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1226M 1222s (1 1165W 1167s (1 1120V
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135s 9 1 Ms1i 122Wbr 147 NH ob(37)
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5.4 Polypeptides 267 glycine residu
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5.4 Polypeptides 269 Raman bands in
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5.4 Polypeptides 271 Figure 5-7. St
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Frequency (cm-'1 100% b 700 500 300
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5.4 Polypptidt~s 215 Table 5-9. Obs
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~~ ~~ ~~~ ~ ~ ~~ 5.4 Polypeptides 2
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5.4 Poliyeptides 219 Table 5-11. Co
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Table 5-12. Aniide mode frequencies
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1351 Lifson, S., Stern, P. S., J. C
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5.6 Refeverices 285 [130] Tiffany,
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Index Amide modes 249 Amorphous pol
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Step-scan FTIR spectroscopy 14,34 -
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