Modern Polymer Spect..

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5.3 Amidc Modes 255 Figure 5-1. Optimized confonxatioiis of Ala dipeptide (p, ti/ in parentheses). Peptide groups-1: C6N7, 7: C12N17. Hydrogen bonds are indicated by broken lines. (From [33]) alter this: for C5, even though the CO sl force constant (1 1.040) is larger than the CO s2 force constant (10.922), the predominantly CO sl mode is at a lower frequency (1 668 cm-') than CO s2 (1 698 cm-I). This is also counterintuitive in terms of the (admittedly weak) hydrogen bond to C02, whereas the relative frequencies are in the expected order for C7E and C7A. In distinction to the nonhydrogenbonded structures, NH ib is now a significant component of the amide I modes of the hydrogen-bonded structures (C7E and C7A). (To a lesser extent, this is also true for the Ala dipeptide in a crystal conformation similar to that of C5 but in which both peptide groups are fully hydrogen bonded [74].) The amide I1 mode frequencies generally reflect the influence of hydrogen bonding, which manifests itself primarily through the magnitudes of such force constants as NH ib and CN s. (It should be noted that explicit hydrogen bond coordinates are not included in the coordinate basis [33, 341, so the force constants implicitly reflect the influence of this interaction.) As expected, the higher frequency modes are associated with the peptide group having a hydrogen-bonded NH. In addition, the modes in C5 involve coupled NH ib displacements [34], which makes it difficult in general to infer the explicit dependence of amide I1 on conformation. The amide I11 modes demonstrate an increasing complexity compared with the
~ Table 5-3. Some aniide modes of three hydrogen-bonded conformers of the alanine dipeptide". N ul Mode Conformer" I 1698 CO s2(47)" CO sl(34j I1 1557 NH ib2(49) CN s2(28j 111 1276 CN sl(23) NH ibl(20) CN s2(14) CO ibl(l1) c5 1668 CO sl(52) CO s2(32) 1525 NH ibl(49) CN sl(251 NH ib2(12) 1229 H" b2(40) CN s2( 14) C7E 1704 1676 CO ~2164) CO sl(70) NH ib2(26) NH ibl(15) C7 A 3 1699 1682 2- CO s2(51) CO sl(55) E. NH ib2(231 CO ~2119) CO sl(14) NH ibl(l51 2 $ 1587 1534 1594 1551 P" c1 NH ib2(59) NH ibl(60) NH ib2(59) NH ibl(601 Y CN s2(27) CN sl(28) CN s2(28) CN sl(27) 2 c, co s2(21) co sl(14) CO s2( 18) CO sl(14) 0 ?$ 1279 1258 1335 1325 1292 H" bl(28) CN s2(31) H" b2(30) H' bl(26) CN ~1137) CN ~1123) H" b2120) CN s2( 13) CN s2(19j CO ib(16) NH ibl(16) H" b1116) H" bl(12) H' b2(18) MC s(12) NM s(13) C"C s(13j 1 bl % 2 c V 693 NH ob1132) CN tl(23) CO ib21 15 i NC" t( 14) 683 NH obl(39) CN tl(35) NC" t(24) CO ob2(14) 585 754 577 809 58 1 NH ob2(111) NH ob2(51) NH obl(102) NH ob2(51) NH oblill6) CN t2( 57) CN t2(40) CN tl(76) CN t2( 19) NC' t(951 NC" t(67) CN tl(8ll r; a From [34]. q, $ 4 5: -166", 167": C7E: -85", 73'; C7A: 75", -62". s: stretch, ib: in-plane bend, b: bend, ob: out-of-plane bend, t: torsion, d: deformation, M: methyl C. Group coordinates defined in [34]. Contributions 2 10.
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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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Page 222 and 223: 4 Vibrational Spectroscopy of Intac
Page 224 and 225: 4.3 Georrietvy oj Intuct Po1vniev.r
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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
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Page 240 and 241: 4.7 Poly(y-phenylene) 225 Figure 4-
Page 242 and 243: Table 4-4. Observed Raman frequenci
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Page 246 and 247: under various models. According to
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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
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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 272 and 273: 5.4 Polypeptides 257 nonhydrogen-bo
Page 274 and 275: 5.4 Polvpeptida 259 Figure 5-2. Ant
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
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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