Modern Polymer Spect..

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1.7 Coizclirsions 29 derived in a straightforward manner. Using this generalized method, the 2D correlation analysis of any time-dependent spectral signals can be carried out. Highly nonlinear time-dependent reactions of crosslinking polymer systems, for example, are followed by the time-resolved IR measurement [65, 661. The resulting sets of time-dependent IR spectra can be transformed into 2D correlation spectra to yield valuable information to probe details of curing reactions of polymers. One of the very promising new developments in the recent 2D correlation analysis of polymers is the application of this versatile technique to the study of spectral changes recorded as functions of a general physical variable, which is no longer limited to time. For example, it is possible to apply the 2D correlation analysis to the near-IR spectral changes corresponding to the development of disorder in a hydrogen-bonded polyamide system induced by the rising temperature [67]. Of course, spectral changes of polymers induced by other variables, such as pressure, age, composition, and the like, may be analyzed in the same way. 1.7 Conclusions 2D IR spectroscopy based on the correlation analysis of the individual timedependent behavior of localized characteristic reorientational motions of various submolecular moieties comprising a system has been shown to be very useful for a broad range of applications in the study of complex polymeric materials. In 2D IR, the spectral resolution is substantially enhanced by spreading the overlapped IR bands along the second dimension. The presence or lack of chemical interactions or connectivity among functional groups located in various parts of the polymer system are detected. The relative reorientation directions and the order of realignment sequence of submolecular units are also provided. Notable discoveries made through the use of 2D IR spectroscopy include the fact that local dynamics of side groups can proceed independent of the polymer main chain, and there can be abrupt changes in the side group realignment mechanism above and below the glass transition temperature. It is possible to probe the niicroscopic spatial distribution of submolecular components of polymers, especially in phase-separated systems such as semicrystalline polymers and block copolymers, and the degree of interactions between various components can be estimated. Specific interactions between Components in polymer mixtures are quite effectively identified. The application of 2D IR spectroscopy certainly is not limited to the characterization of traditional synthetic polymers. Complex macromolecules of biological origin can also be readily studied by this technique. The recent extension of the 2D correlation concept to (1) spectroscopic study of polymers using probes other than IR, (2) nonsinusoidally varying spectral changes, and 13) dependence on physical variables other than time has greatly expanded the scope of possible spectroscopic applications of this technique to the study of polymeric materials.
30 I T~.vo-Dii7iensioiiLiI Infmr-ed (2D IR) Spectroscopji 1.8 Symbols and Abbreviations A All AL A 0 p2 D Dm DIRLD T t AA AAW AA AA AA’ AA” 0 X Y CI P I & & V 8 T a) 0 Absorbance Parallel absorbance Perpendicular absorbance Structural absorbance =All + 2Al Orientation factor Dichroic ratio = Ai,/Al Ultimate dichroic ratio Dynamic infrared 1inea.r dichroism Observation period Time Dichroic difference 5 All - A1 Ultimate dichroic difference Dynamic dichroic difference Amplitude of dynamic dichroic difference In-phase dynamic dichroic difference E AA cos P Quadrature dynamic dichroic difference = AA sin p Synchronous correlation intensity Two-dimensional cross-correlation function Asynchronous correlation intensity Transition dipole orientation angle Dynamic dichroism phase angle Dynamic strain Dynamic strain amplitude Wa ven urn ber Polymer chain segment orientation angle Correlation time Frequency of dynamic strain / dynamic dichroism Spatial average 1.9 References [l] Noda, I. Bd. Am. Plzys. SOC. 1986, 31, 520. [2] Noda, I. .I. Am. Cliem. SOC. 1989, Ill, 8116. [3] Noda, I. Appl. Spectrox. 1990. 44, 550. [4] Noda, I. Clierrifracfs-l~fflcromof. Ed 1990, I , 89. 151 Palmer, R. A.; Manning, C. J.; Chao. J. L.; Noda, 1.; Dowrey, A. E.; Marcott, C. Appl. SiJeCtrO,SC. 1991, 45, 12. 161 Marcott, C.; Dowrey, A. E.; Noda, I. Aridj;t. C/zem. 1994, 66, 1065A. [7] Marcott, C.; Dowi-ey, A. E.: Noda. 1. A~JJ/. Spectrosc. 1993, 47, 1324. [8] Noda, I. Appl. Spectrosc,. 1993, 47, 1329.
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 10 and 11: Contents 1 Two-Dimensional Infrared
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 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
Page 60 and 61: 2.5 Electric Field-Itzduced Orienta
Page 62 and 63: 2.5 Electric Field-IwrElrced Orient
Page 64 and 65: 2.5 Electric Field-Im/irced Orientu
Page 66 and 67: 2.5 Electric Field-Induced Orientli
Page 68 and 69: 2.5 Electric Field-Induced Orientat
Page 70 and 71: 2.5 Electric Field-Induced Orienfat
Page 72 and 73: 2.5 Elrc tric Field-Iiidircwl Orim
Page 74 and 75: 2500 2008 I s00 WRVtNdMRtR CM-I Fig
Page 76 and 77: -3.6 Aligmient OJ' Side- Clinin Liy
Page 78 and 79: ~ polyester 2.6 Alignnient qf Side-
Page 80 and 81: I." 0.9 0.8 Figure 2-34. FTlR 0.7 p
Page 82 and 83: induced alignment of the investigat
Page 84 and 85: 2.7 Orientation oj Liquid Ci:i,stal
Page 86 and 87: 2.7 Orieritation of Liquid Ciysttrl
Page 88 and 89: 0 8 18 16 1 a W u z a m a 0 Ln m Q
Page 90 and 91: 2.7 Orientation oj Liquid Crystals
Page 92 and 93: 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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