Modern Polymer Spect..

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~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 801 Table 4-3. Vibrational frequencies (in cm-') of neutral polyi p-phenylenei and its "C-substituted and perdeuterated analogs. Sym- No. Normal species '3C-substituted Perdeuterated analog metric analog species Observed Cnlculated Observed Calculated Observed Calculated 1831 [84] [43] [86] [87] [83] [841 ~ 4 1 1841 1871 1595 1282 1222 798 - 1482 1048 1000 - 1401 I254 1081 - 624 809 ~ ~ ~ ~ 1599 1626 1661 1601 1541 1295 1282 1289 1290 1239 1226 1233 1127 1184 1209 776 792 846 802 768 969 951 961 ~ 427 367 401 - - 831 823 834 1477 1487 1510 1490 1452 1060 1045 1051 1044 - 991 984 968 1004 965 945 968 945 ~ 768 754 760 - 441 410 402 1407 1399 1440 1412 1361 1232 1275 1268 1343 ~ 1119 1162 1075 1118 ~ 1603 1601 1654 1652 - 1290 1325 1328 1343 633 625 602 616 602 487 488 460 418 ~ 198 797 790 ~ 497 457 458 - - 1547 1563 1246 1255 1216 892 741 764 960 ~ 415 ~ 825 ~ 1445 1354 1035 817 958 978 936 ~ 742 ~ 426 ~ 1375 1338 1 I93 - 1092 ~ 1546 ~ 1277 - 610 606 470 - 789 650 48 1 ~ 1563 1572 1281 1253 881 863 751 776 775 ~ 378 - 647 ~ 1353 1364 812 811 984 977 824 ~ 663 - 414 ~ 1334 1347 1185 1268 854 855 1579 1620 1016 1044 600 593 450 383 661 ~ 435 - Rainan spectrum of neutral poly( p-phenylene) is well explained by the effectiveconjugation-coordinate model [95]. 4.7.2.2 Doped Poly(p-phenylene) and the Radical Anions and Dianions of p-Oligophenyls The Raman spectra of heavily Na-doped poly( y-phenylene) measured with the 488.0, 514.5, 632.8, 720, and 1064 nm laser lines are shown in Figure 4-13 [70]. The Raman spectra of Na-doped poly( p-phenylene) are apparently different from that of intact poly( p-phenylene), indicating that these bands arise from charged domains (i.e., negative polarons and/or negative bipolarons) created by Na-doping. The assignments of these bands will be discussed on the basis of the data for the radical anions and dianions of p-oligophenyls.
224 4 Vibrcitioiznl <strong>Spect</strong>roscopy of Intact and Doped Conjugated <strong>Polymer</strong>s RAMAN SHIFT/cm-' Excitation wavelength is 1064 nin [88] Figure 4-12. Atomic displacements of inajor vibrational modes (k = 0) of poly(p-phenylene). (a) 1599 an-' [v2(ng)]; (b) 1295 cm-' [q(ug)];(c) 1226 cm-I [114(a,)]: (d) 776 cm-I [v5(az)]: (d) (el (f) (e) 1477 c1n-l [1~,0(b,~)]; (f) 991 c1n-l [iy(hlu)][84] The Raman spectra of the radical anions of PP2 [92, 96, 971, PP3 [70, 981, PP4 [70, 981, PP5 [70] and PP6 [70], and the diaiiions of PP3 [70, 981, PP4 [70, 981, PP5 [70], and PP6 [70] have been reported by several authors. The Raman spectra of the radical anions (PPnP) and dianions (PPTz~~) in THF solutions are shown in Figures 4-14 and 4-15, respectively. The excitation wavelengths used are rigorously or nearly resonant with band I1 of the radical anions and band I' of the dianions. The Raman spectra of the radical anions are similar to each other, and so are the Rainan spectra of the dianions. However, the two groups of the Raman spectra are different from each other and from those of neutral 12-oligopheiiyls. These results suggest that the negative polarons and bipolarons, corresponding respectively to the radical anions and dianions, can be identified by Raman spectroscopy. The Ranian spectra of the radical anions in Figure 4-14 show siiiall changes with
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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
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3 9 Mouiiiq ToIvmds Rerrlitv: From
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3.9 Moving Towards Reality: From Or
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3.9 Moving Towards Reality: Froin O
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3.10 Wlmt Do We Learn from Cnlcailc
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+ 3.11 A Very Siriiple Ccrse: Latti
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3 I1 A Yey) Siiiiple Case: LLittice
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3.11 A Vq> Siiiiplc Crrw: Luttice D
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Figure 3-22. Sample eigenvectors in
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3.12 CIS-trans Opening @the Double
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3.13 Defect Modes cis Structtrr.al
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3.13 Defect Mo&s cis Structurcil Pr
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0 3.14 Case Studies N 0 d - Y N o m
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3.14 Case Studies 147 OC 60 58 57.
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3.14 Case Studies 149 GI A V E N U
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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
Page 188 and 189: 3.18 Band Broadening and Confonnati
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
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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
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Page 212 and 213: 3.19 A Worked Example 197 existence
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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
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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
Page 236 and 237: is worthwhile pointing out that the
Page 240 and 241: 4.7 Poly(y-phenylene) 225 Figure 4-
Page 242 and 243: Table 4-4. Observed Raman frequenci
Page 244 and 245: 4.8 Other Polwieys 229 Table 4-5. T
Page 246 and 247: under various models. According to
Page 248 and 249: 4. I0 Mechnriism oj Charge. Transpo
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Page 252 and 253: 4.12 References 237 [98j Matsunuma,
Page 254 and 255: 5 Vibrational Spectroscopy of Polyp
Page 256 and 257: 5.2 FOYCC Fields 241 such calculati
Page 258 and 259: 5.2 Force Fields 243 accounts for o
Page 260 and 261: 5.2 Force Fields 245 centers of the
Page 262 and 263: 5.2 Force Fields 247 ture with conf
Page 264 and 265: 5.3 Amide Modes 249 to the nh initi
Page 266 and 267: 5.3 Ainide Modes 251 Table 5-1. Ami
Page 268 and 269: Table 5-2. Some amide modes of four
Page 270 and 271: 5.3 Amidc Modes 255 Figure 5-1. Opt
Page 272 and 273: 5.4 Polypeptides 257 nonhydrogen-bo
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Page 276 and 277: I 5.4 Polypeptides 261 )I .- + $ 80
Page 278 and 279: 1226M 1222s (1 1165W 1167s (1 1120V
Page 280 and 281: 135s 9 1 Ms1i 122Wbr 147 NH ob(37)
Page 282 and 283: 5.4 Polypeptides 267 glycine residu
Page 284 and 285: 5.4 Polypeptides 269 Raman bands in
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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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