Modern Polymer Spect..

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I 5.4 Polypeptides 261 )I .- + $ 800 1000 1200 1400 1500 1600 1700 0 1 1 1 2800 2900 3000 3100 3200 3300 3400 Figure 5-4. Infrared spectra of /l-poly(Lalanine). Upper two panels: mid-IR region. (-) Electric vector perpendicular to the stretching direction. (- - -) Electric vector parallel to the Stretching direction. (From [SS]) Lower panel: far-IR region. (From [86]) Frequency (ern-') 2 0) 1 Figure 5-5. Ranian spectrum of /l-poly(L alanine). (From [SS]) 900 800 700 600 500 400 300 200 100 FREQUENCY (cm-' ma1 mode analysis [22] are given in Table 5-6 (the NH s modes, which are influenced significantly by Fernii resonances 1901, and the CH s modes are discussed in an earlier paper [SO]). There are some general points to note about this normal mode analysis. First, the
Table 5-6. Observed and calculated frequencies (in cm-' ) of APPS poly(L-alanine). Observed" Calculated Potential energy distributionh Raman IR A Bi B2 Bi 1669s 1553VW 1538W 1451s 1451s 1399W 1368W 1335W 1311W 12433 1694W 1 1 1632VS I 1555MW I 15248 1) 1454s / / 1446s i 1454s 11 1446s _L 1402MW 11 1386W i 1372MW / / 1330W br I 1309 sh 1670 1539 1455 1452 1402 1372 c 1236 1695 1528 1455 1452 1399 1372 1630 1562 1452 1451 1383 1317 1299 1698 1592 1453 1451 1385 1337 1305 CO s(78) CN sf141 CO sf76) CN si19) CO sf73) CN s(21 I CO sf70) CN ~(21) NH ib(571 CN sf211 '2°C s[l01 NH ibi53) CN sf17) C"C ~(14) NH ibi48j CN sf22) CO ibi121 C*C $11) NH ibi41j CN si26) CO ib~141 C"C s(13) CH3 abl(34) CH7 ab2(39) CH3 ab1146) CH7 ab2137) CH-, ablf88) CH? rlfl0) CH; ab1186) CHI rlfl0) CH3 ab2145) CHi dblf43) CH3 ab2(48) CH? ablf41) CHI ab2i861 CH7 12(10) CH? ab2(89) CH7 12j10) H" b2(32) CH7 sb(17) C*C sfl4) NH lbi13) Ha b2f33) CHI sb120) NH ib(l5) C'C sill) CH7 sb(70i H' blil6I CYCD S! 111 CH3 ~b174) H" bl (16, C^Ci'~i10) CH7 sbi64) H'b? (161 CH1 sbi6lI H'b2 119) H" b2132) NH lb(25) C"C ~(12) CH3 sbfll) H" b2164) NH Ibf 15) H" b2130) CN ~(181 CO ibfl9 NH M23) CO ibfl8) C'C si14) CN sf131 H' b2134) NH ibil9) NC' ~(19) CN sil3i
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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
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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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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
Page 236 and 237: is worthwhile pointing out that the
Page 238 and 239: ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ 801 Table 4-3
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
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Page 250 and 251: 4.12 Reftrences 235 [ 131 Kuzmany,
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
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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
Page 274 and 275: 5.4 Polvpeptida 259 Figure 5-2. Ant
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
Page 286 and 287: 5.4 Polypeptides 271 Figure 5-7. St
Page 288 and 289: Frequency (cm-'1 100% b 700 500 300
Page 290 and 291: 5.4 Polypptidt~s 215 Table 5-9. Obs
Page 292 and 293: ~~ ~~ ~~~ ~ ~ ~~ 5.4 Polypeptides 2
Page 294 and 295: 5.4 Poliyeptides 219 Table 5-11. Co
Page 296 and 297: Table 5-12. Aniide mode frequencies
Page 298 and 299: 1351 Lifson, S., Stern, P. S., J. C
Page 300 and 301: 5.6 Refeverices 285 [130] Tiffany,
Page 302 and 303: Index Amide modes 249 Amorphous pol
Page 304 and 305: Step-scan FTIR spectroscopy 14,34 -
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