Modern Polymer Spect..

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3.18 Band Broadening and Confonnational Flexibility 173 Figure 3-42. Hexadeuteropropane: 10- n 0 " d+(CHZ) I I I Figure 3-43. Ranian spectrum in the C-Hstretching range of C~lH44: (a) solid and ib) melt. a 3050 3000 2950 2900 2850 2800 cm-I 1. For short chains, the antysimmetric d- mode broadens in the Raman spectrum by increasing temperature and sometimes shifts upward in frequency (Figure 3-42), while d+ neither shifts substantially nor broadens. (See also Figure 3-37.) 2. For long polymethylene chains and polyethylene at melting, the strong d- modes collapses into a featureless very broad scattering and by increasing temperature shifts its maximum towards higher frequencies (Figure 3-43). 3. For crystalline n-alkanes the width of d- does not increase with teniperature up to a few degrees below melting (Figure 3-44). 4. When n-alkanes are inserted as clathrates in urea channels, the width of d- is
174 3 Vilmitionul Slirctru us ci Probe of Stnictiirul Ortlev Figure 3-44. Evolution with temperature of the Raman spectrum of solid Cl,Hd, in the CH stretching rangc. Notice the behavior with temperature of d+ and d- inodes.
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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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2.5 Electric Field-Induced Orientat
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2.5 Electric Field-Induced Orienfat
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2.5 Elrc tric Field-Iiidircwl Orim
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2500 2008 I s00 WRVtNdMRtR CM-I Fig
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-3.6 Aligmient OJ' Side- Clinin Liy
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~ polyester 2.6 Alignnient qf Side-
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I." 0.9 0.8 Figure 2-34. FTlR 0.7 p
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induced alignment of the investigat
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2.7 Orientation oj Liquid Ci:i,stal
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2.7 Orieritation of Liquid Ciysttrl
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0 8 18 16 1 a W u z a m a 0 Ln m Q
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2.7 Orientation oj Liquid Crystals
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2.7 Orientation of Liquid Crjvtals
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2.7 Orientatioiz of Liquid Crystals
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2.8 Conclusions 81 strain. As A0 is
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3. I0 Refcreiice.r 83 [I 71 Hoffina
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2.10 References 85 [92] Wiesner, U.
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t Order/Disorder in Chain Molecules
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onds which hold atoms together thro
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3.2 The Dyriamical Case qf Simll ar
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3.2 The Dyrinniical Case of Sinnll
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3.4 S11or.f- and Loizg-Rcrizye Vibr
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3.4 Slzort- and Loiig-Range Vibrati
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eyularity), e.g., 2. During the pol
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3.5 Towards Lnrger Molecules: From
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3.5 TOIIYW~ Laiyer Molertiles: Fvoi
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3.5 Towmu" Larger Molecules: F~om O
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1700 - CIO --- ca c 22 _- c 12 l l
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3.6 From Dynamics to Vibrational Sp
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3.6 Froin Dynaiiiics to T’ihratio
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3.7 The Case of Isotactic Polypropy
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3.7 The Cuse of Isotactic Polypvop.
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3.8 Density of Vibrational States a
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3.8 Dtvz.sit,v of L’ihrntioizal S
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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
Page 168 and 169: 3.14 Case Studies 153 (I10 + 200) +
Page 170 and 171: 3.14 Case Studies 155 1500 1480 146
Page 172 and 173: 3.14 Case Studies 157 the molecular
Page 174 and 175: 17E (ir 1, R): (iii) z = 4, t = 1,
Page 176 and 177: 3.16 Stnictural Znlioi~zogeneity an
Page 178 and 179: 3.1 7 Fermi Resonancrs 163 stants.
Page 180 and 181: 3.1 7 Femi Resorinnces 165 2 L 1 29
Page 182 and 183: lowing. The CHl-bending mode 6 [cer
Page 184 and 185: 3.17 Ferini Re.sonrriire.s 169 a Fi
Page 186 and 187: 3. I7 Fernii Resoiiances 17 1 terin
Page 190 and 191: 3.18 Bmd Brourleiziriy md Cmforrnat
Page 192 and 193: 3.18 Band Bvoaderiing arid Conjonna
Page 194 and 195: 3.18 Band Broadening and Confornmti
Page 196 and 197: 3.19 A Worked E.utinple 181 pre-mel
Page 198 and 199: 3.19 A Wovh-ecl E.uanzple 183
Page 200 and 201: 3.19 A Worked Example 185 19 5°C 2
Page 202 and 203: 3.19 A Workrd Example 187 Figure 3-
Page 204 and 205: 3.19 A Worked E.rcnniplr 189 LAM I
Page 206 and 207: 3.19 A Worked E.xuniple 191 Figure
Page 208 and 209: 3.19 A Worked E.vnn~yle 193 Figure
Page 210 and 211: 3.19 A Worked E.vnrqde 195 009.1 00
Page 212 and 213: 3.19 A Worked Example 197 existence
Page 214 and 215: 3.1 9 A Worked Example 199 The soli
Page 216 and 217: 3.20 References 201 very important,
Page 218 and 219: 3.20 References 203 [41] M. Gussoni
Page 220 and 221: 3.20 Refeeveiicrs 205 [I 171 P. Jon
Page 222 and 223: 4 Vibrational Spectroscopy of Intac
Page 224 and 225: 4.3 Georrietvy oj Intuct Po1vniev.r
Page 226 and 227: 1'45 4.4 Geometric Chunges I?zditce
Page 228 and 229: 4.4 Geometric Chmges Iiid~lrcecl bj
Page 230 and 231: 4 5 Mer1iodolog.v of Raiii~11 Studi
Page 232 and 233: 4.7 Poly(p-pheiq.lene) 217 with an
Page 234 and 235: 4.7 Pol)~(p-pheiz~~lene) 219 ENERGY
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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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Modern Polymer Spect..

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