Modern Polymer Spect..

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Contents 1 Two-Dimensional Infrared Spectroscopy I. Noda, A. E. Downrey and C. Marcott 1.1 Introduction 1.2 Background 1.3 Basic Properties of 2D Correlation Spectra 1.4 Instrumentation 1.5 Applications 2 Segmental Mobility of Liquid Crystals and Liquid-Crystalline Polymers Under External Fields: Characterization by Fourier-Transform Infrared Polarization Spectroscopy H. W. Siesler, I. Zebger, Ch. Kulinna, S. Okretic, S. Shilov and U. Hoflinann 2.1 Introduction 2.2 Measurement Techniques 2.3 Theory 2.4 Structure Dependent Alignment of Side-Chain Liquid-Crystalline Polyacrylates on Anisotropic Surfaces 2.5 Electric-Field Induced Orientation and Relaxation of Liquid-Crystalline Systems 2.6 Alignment of Side-Chain Liquid-Crystalline Polyesters Under Laser Irradiation 2.7 Orientation of Liquid-Crystals Under Mechanical Force 2.8 Conclusions 1 1 2 10 12 15 33 33 34 36 37 38 60 67 81 3 Vibrational Spectra as a Probe of Structural Order/Disorder in Chain Molecules and Polymers 87 G. Zerbi and M. Del Zoppo 3.1 Introduction 87 3.2 The Dynamical Case of Small and Symmetric Molecules 88 3.3 How to Describe the Vibrations of a Molecule 94 3.4 Short and Long Range Vibrational Coupling in Molecules 95 3.5 Towards Larger Molecules: From Oligoiners to Polymers 98 3.6 From Dynamics to Vibrational Spectra of One-Dimensional Lattices 107
X Corztrnts 3.7 The Case of Isotactic Polypropylene: A Textbook Case 3.8 Density of Vibrational States and Neutron Scattering 3.9 Moving Towards Reality: From Order to Disorder 3.10 What Do We Learn from Calculations 3.11 A Very Simple Case: Lattice Dynamics of HCI-DCl Mixed Crystals 3.12 Cis-Tram Opening of the Double Bond in the Polymerisation of Ethylene 3.13 Defect Modes as Structural Probes in Polymethylene Chains 3.14 Case studies: Case 1 Conformational Mapping of Fatty Acids Through Mass Defects Case 2 Liquid Crystalline Polymers: Polyesters Case 3 Chain Folding in Polyethylene Single Crystals Case 4 The Structure of the Skin and Core in Polyethylene Films (Normal and Ultradrawn) Case 5 Moving Towards More Complex Polymethylene Systems 3.15 Simultaneous Configurational and Conformational Disorder. The case of Polyvynylchloride 3.16 Structural Inhomogeneity and Raman Spectroscopy of LAM Modes 3.17 Fermi Resonances 3.18 Band Broadening and Conformational Flexibility 3.19 A Worked Out Example: Froin N-Alkanes to Polyethylene. Structure and Dynamics 4 Vibrational Spectroscopy of Intact and Doped Conjugated Polymers and Their Models Y Furukawa and M. Tasuiiii 4.1 Introduction 4.2 Materials 4.3 Geometry of Intact Polymers 4.4 Geometrical Changes Introduced by Doping 4.5 Methodology of Raman Studies of Polarons, Bipolarons and Solitons 4.6 Near Infrared Raman Spectroscopy 4.7 Poly(p-phenylene) 4.8 Other Polymers 4.9 Electronic Absorption and ESR Spectroscopies and Theory 4.10 Mechanism of Charge Transport 4.1 1 Summary 5 Vibrational Spectroscopy of Polypeptides S. Kvinim 5.1 Introduction 113 1 I7 122 128 131 138 141 144 146 147 150 152 156 158 159 163 172 180 207 207 208 209 210 215 216 217 228 230 23 1 234 239 239
Page 2 and 3: Modern Polymer Spectroscopy Edited
Page 4 and 5: Modern Polymer Spectroscopy Edited
Page 6 and 7: Preface For unfortunate reasons the
Page 8 and 9: However, theory and calculations yi
Page 12 and 13: Con ten t~ xi Index 5.2 Force Field
Page 14 and 15: Contributors M. Del Zoppo Dipartime
Page 16 and 17: 1 Two-Dimensional Infrared (2D IR)
Page 18 and 19: 1.2 Brick~qrorrnrl 3 . Figure 1-3.
Page 20 and 21: 1.0 , Figure 1-6. The in-phtrse and
Page 22 and 23: 1.2 Bcrckgroinizd 7 where AA (i~) i
Page 24 and 25: 1.2 Background 9 1.2.5 Two-Dimensio
Page 26 and 27: 1.3 Bnsic Properties of 20 IR Corre
Page 28 and 29: 2D IR spectrometer coupled with a d
Page 30 and 31: 1.5 Applirtrtions 15 Unlike a dispe
Page 32 and 33: \ '\ Melliyleiie 1'7- -3000 Posiliv
Page 34 and 35: 11 Amorphous Crystalline ,...." I F
Page 36 and 37: 1.5 Applications 21 / I 1430 Figure
Page 38 and 39: 1.5 Appliccitioiis 23 Methylene Fig
Page 40 and 41: 1.5 Ajqdicrrtions 25 3024 Figure 1-
Page 42 and 43: 1.5 Applicutions 27 Furthermore. th
Page 44 and 45: 1.7 Coizclirsions 29 derived in a s
Page 46 and 47: 1.9 References 31 [9] Colthup, N. B
Page 48 and 49: 2 Segmental Mobility of Liquid Crys
Page 50 and 51: SRMPLE/DETECTOR e3 ‘retardation
Page 52 and 53: 2.4 Srvuc me-Dependenr Alignment 37
Page 54 and 55: 2.5 Electric Field-Innductid Orirnt
Page 56 and 57: 2.5 Electric Field-nclticetl Orient
Page 58 and 59: 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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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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