INTRODUCTION TO INFRARED AND RAMAN SPECTROSCOPY

THIRD EDITION

Norman B. Colthup
*', " !*",,

Lawrence H. Daly

Stephen E. Wiberley

ACADEMIC PRESS, INC.

Harcourt Brace Jovanovich, Publishers

Boston San Diego New York London Sydney Tokyo Toronto

CONTENTS
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'

txi.

PREFACE

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Chapter 1 VIBRATIONAL AND ROTATIONAL SPECTRA

1.1 Introduction, 1; 1.2 Photon Energy, 2; 1.3 Degrees of Freedom of Molecular Motion, 3; 1.4 Normal Modesof Vibration, 4; 1.5 Mechanical Molecular Models, 4; 1.6 Coordinates Used to Describe Molecular Vibrations, 6; 1.7 Classical Vibrational Frequency Formula for Diatomic Molecule, 7; 1.8 Infrared Absorption and the Change in Dipole Moment, 11; 1.9 Anharmonicity and Overtones, 15; 1.10 Vibrational Potential Function, 16; 1.11 Introduction to the Quantum Effect, 19; 1.12 The Quantum Mechanical Harmonie Oscillator, 23; 1.13 The Boltzmann Distribution Function, 25; 1.14 Vibrational Transitions and Infrared Absorption, 26; 1.15 The Anharmonic Oscillator, 27; 1.16 Cqmbination and Difference Bands, 30; 1.17 Fermi Resonance, 31; 1.18 Rotation of Linear Molecules, 33; 1.19 Rotational Transitions and Infrared Absorption, 37; 1.20 The Nonrigid Rotator, 41; 1.21 Rotational Line Intensities, 42; 1.22 Types of Rotators, 43; 1.23 Rotation of Symmetrie Top Molecules, 45; 1.24 Vibrational-Rotational Spectrum, Classical Picture, 46; 1.25 Vibrational-Rotational Spectrum, Quantum Mechanical Treatment, 48; 1.26 Vibrational-Rotational Spectrum, Nonrigid Rotator, 54; 1.27 Spherical Top Molecules, 56; 1.28 Symmetrical Top Molecules, 56; 1.29 Asymmetrical Top Molecules, 58; 1.30 The Raman Effect, 60; 1.31 Polarizability, 62; 1.32 The Tensor Character of the Polarizability, 65; 1.33 Depolarization Ratio, 68; 1.34 Pure Rotational Raman Spectra, 70; 1.35 Raman Sources, 72

Chapter 2 IR EXPERIMENTAL CONSIDERATIONS

2.1 Source of Infrared Radiation, 75; 2.2 Infrared Detectors, 77; 2.3 Monochromators, 77; 2.4 Interferometers, 80; 2.5 Infrared Transmitting Materials, 83; 2.6 Salt Polishing, 84; 2.7 Infrared Cells, 85; 2.8 Solid Sampling, 87; 2.9 Internal Reflection Spectroscopy, 92; 2.10 Polarized Infrared Radiation, 94; 2.11 Quantitative Analysis, 100
V

CONTENTS

Chapter 3 MOLECULAR SYMMETRY

3.1 Symmetry Properties, 109; 3.2 Point Groups, 115; 3.3 Group Theory, 119; 3.4 Group Theory Applied to Point Groups, 121; 3.5 Representations of Groups, 124; 3.6 Irreducible Representations, 129; 3.7 The Character Table, 131; 3.8 Irreducible Representation Components in a Representation, 136; 3.9 Transformation Properties of a Vector, 138; 3.10 The Numberof Fundamentals ofEach Type, 139; 3.11 Selection Rules, 141; 3.12 Infrared Activity of Fundamentals, 144; 3.13 Raman Activity of Fundamentals, 145; 3.14 Overtone and Combination Bands, 146; 3.15 Symmetry Coordinates, 150; 3.16 Isotope Effects and the ProductRule, 152; 3.17 Character Tables and Selection Rules, 155

Chapter 4 THE VIBRATIONAL ORIGIN OF GROUP FREQUENCIES

4.1 Introduction, 171; 4.2 Diatomic Oscillators, 172; 4.3 Coupled Oscillators, 172; 4.4 Unsymmetrical Coupled Oscillators, 175; 4.5 XH Stretching Frequencies, 177; 4.6 Triple Bond Vibrations, 178; 4.7 Cumulated Double Bonds, 180; 4.8 The Linear M,M2M3 Model, 181; 4.9 XC=N Compounds, 182; 4.10 Carbonyl and C = C Compounds, 184; 4.11 Cyclic Compound Stretching Vibrations, 188; 4.12 The Bent M,M2M, Stretching Frequencies, 192; 4.13 Noncyclic Single Bond Vibrations, 194; 4.14 Bend-Bend Interaction, 196; 4.15 Bend-Stretch Interaction, 202; 4.16 Multiple Oscillator Groups, 207; 4.17 Interaction Force Constant Effects, 208; 4.18 Hydrogen Bonding, 210

Chapter 5 METHYL AND METHYLENE GROUPS

5.1 Introduction to Group Frequencies, 215; 5.2 Methyl Groups, 216; 5.3 CH3 Stretching Vibrations, 217; 5.4 CH3 Deformation Vibrations, 222; 5.5 CH3 Rock Vibrations, 225; 5.6 Methylene Groups, 227; 5.7 CH2 Stretching Vibrations, 228; 5.8 CH2 Deformation Vibrations, 228; 5.9 CH2 Wag Vibrations, 228; 5.10 CH2 Rock Vibrations, 230; 5.11 CH2 Twisting Vibrations, 232; 5.12 CH2 in Cyclic Compounds, 232; 5.13 Carbon Hydrogen Group, 233

CONTENTS

Vll

Chapter 6 TRIPLE BONDS AND CUMULATED DOUBLE BONDS

6.1 Introduction, 235; 6.2 Monosubstituted Acetylenes, 236; 6.3 Disubstituted Acetylenes, 237; 6.4 Allenes, 238; 6.5 Nitriles, 238; 6.6 Nitrile /V-Oxides and Complexes, 239; 6.7 Cyanates, 239; 6.8 Isocyanates, 239; 6.9 Thiocyanates, 240; 6.10 Isothiocyanates, 240; 6.11 Nitriles on a Nitrogen Atom, 240; 6.12 Carbodiimides, 241; 6.13 Ketene Imines, 241; 6.14 Diazo Compounds, 241; 6.15 Azides, 243; 6.16 Aryl Diazonium Salts, 243; 6.17 Isocyanides, 244; 6.18 Ketenes, 244; 6.19 Cyanide Ions, 244; 6.20 Cyanate Ions, 245; 6.21 Thiocyanate Ions, 245; 6.22 Metal Carbonyls, 245; 6.23 Three and Four Cumulated Double Bonds, 245

235

Chapter 7 OLEFIN GROUPS

7.1 Noncyclic Olefins, 247; 7.2 Olefinic Hydrogen Wagging Vibrations, 252; 7.3CyclicC = C, 257

247

Chapter 8 AROMATIC AND HETEROAROMATIC RINGS

8.1 Benzene Rings, 261; 8.2 The Carbon-Carbon Vibrations, 263; 8.3 The 1600 cm1 Region, 264; 8.4 The 1500 cm"1 Region, 266; 8.5 The 700 cm' Region, 267; 8.6 The 900-700 cm r CH Wag Bands, 268; 8.7 The 2000-1650 cm1 Summation Bands, 275; 8.8 The 1300-1000 cm' Region, 276; 8.9 The 850-600 cm' Region, 279; 8.10 The 550-400 cm ' Region, 280; 8.11 Condensed Ring Aromatic Compounds, 281; 8.12 Pyridines, 283; 8.13 Pyridine N-Oxides, 283; 8.14 Pyrimidines, 284; 8.15 Triazines, 284; 8.16 Alkyl- or Aryl-Substituted Triazines, 284; 8.17 Melamines and Guanamines, 285; 8.18 Chloro-, Oxy-, and Thio-Substituted Triazines, 285; 8.19Tetrazines, 286; 8.20HeteroaromaticFive-Membered Ring Compounds, 286; 8.21 Cyclopentadienyl Ring-Metal Complexes, 288

261

Chapter 9 CARBONYL COMPOUNDS

9.1 Introduction, 289; 9.2 Mass Effects, 289; 9.3 Bond Angle Effects, 292; 9.4 Inductive Effects, 293; 9.5 Mesomeric Effects, 294; 9.6Ketones, 295; 9.7 a-Chloro Ketones, 295; 9.8 Conjugated Ketones, 296; 9.9 Conjugated Hydrogen Bonded Ketones, 297; 9.10 Bond Angle Effects in

289

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CONTENTS

Ketones, 299; 9.11 Aldehyde CH Vibrations, 300; 9.12 Aldehyde Carbonyl Vibrations, 301; 9.13 Aldehyde CC, 301; 9.14 Ester C = 0, 301; 9.15 Ester CO, 302; 9.16 Out-of-Plane Hydrogen Vibrations in Unsaturated Esters, 305; 9.17 Groups Next to the Carbonyl in Esters, 306; 9.18 Groups on the Oxygen Atoms in Esters, 307; 9.19 Lactones, 307; 9.20 Thiol Esters and Related Compounds, 308; 9.21 Organic Carbonate Derivatives and Related Compounds, 309; 9.22 Oxalates, 310; 9.23 Anhydrides, 310; 9.24 Peroxides, Acyl or Aroyl, 312; 9.25 HalogenSubstituted Carbonyls, 312; 9.26 Carboxylic Acid OH Stretch, 313; 9.27 Carboxyl-Carbonyl Stretch, 313; 9.28 Carboxyl OH Bending and CO Stretching, 315; 9.29 Monomeric Acids, 315; 9.30 Aliphatic Peroxy Acids, 316; 9.31 Aromatic Acids, 316; 9.32 Aliphatic Bands in Long Chain -Aliphatic Carboxylic Acids, Ester, and Soaps, 317; 9.33 Carboxyl Salts, 317; 9.34 Amino Acids, 318; 9.35 Amido Acids, 319; 9.36 Unsubstituted Amides, 319; 9.37 /V-Substituted Amides (trans), 320; 9.38 /V-Substituted Amides (eis) (Lactams), 321; 9.39 Disubstituted Amides, 322; 9.40 Ureas, 322; 9.41 Carbamates, 323; 9.42 Hydroxamic Acids, 323; 9.43 Imides, 323; 9.44 Isocyanurates, 324; 9.45 Acid Hydrazides, 325

Chapter 10

ETHERS, ALCOHOLS, AND PHENOLS

10.1 Aliphatic Ethers, 327; 10.2 Aromatic Ethers, 328; 10.3 Vinyl Ethers, 329; 10.4 Cyclic Ether Linkages, 331; 10.5 Oxirane Ring Compounds, 331; 10.6 OH Stretch in Alcohols and Phenols, 332; 10.7 CO Stretch, 333; 10.8 OH Deformation, 334; 10.9 Phenols, 334; 10.10 Noncyclic Acetals and Related Compounds, 335; 10.11 Cyclic Acetals, 335; 10.12 Carbohydrates, 335; 10.13 Peroxides, 336

327

Chapter 11 AMINES, C = N, AND N = 0 COMPOUNDS 339

11.1 NH2 Stretch in Amines, 339; 11.2 NH2 Deformation in Amines, 340; 11.3 NH, 340; 11.4 CN in Aliphatic Amines, 341; 11.5 CN in Aromatic Amines, 341; 11.6 Aliphatic Bands in Amines, 342; 11.7 The Ammonium Ion, 343; 11.8 Amine Salts, 343; 11.9 C = N Groups, 344; 11.10 Nitro Group, 346; 11.11 Organic Nitrates, 349; 11.12 Nitramines, 349; 11.13 Organic Nitrates, 350; 11.14 Inorganic Nitrates and Nitrites, 350; 11.15 N = N Azo, 350; 11.16 Azoxy and Azothio Groups, 352; 11.17 C-Nitroso Compounds, 353; 11.18 Nitrosamines, 354

CONTENTS

IX

Chapter 12 COMPOUNDS CONTAINING BORON, SILICON, PHOSPHORUS, SULFUR, OR HALOGEN

12.1 Boron Compounds, 355; 12.2 BO, 355; 12.3 BOH, 356; 12.4 B - N , 356; 12.5 BH, 357; 12.6 B - C l , 357; 12.7 BCH 358; 12.8 BPhenyl, 358; 12.9 Silicon Compounds, 358; 12.10 SiH, 359; 12.11 SiCH3, 360; 12.12 S i - C H 2 - R , 360; 12.13 SiC6H 360; 12.14 SiCH = CH2, 360; 12.15 SiOR, 361; 12.16 SiOCH5, 361; 12.17 SiOSi, 361; 12.18 SiOH, 361: 12.19 SiHalogen, 362; 12.20 SiN, 362; 12.21 Phosphorus Compounds, 362; 12.22 PH, 363; 12.23 P = 0, 364; 12.24 POH, 365; 12.25 POP, 365; 12.26 P0 2 -, POS", P0 3 2 , P0 4 3 , 366; 12.27 POC (Aliphatic), 366; 12.28 POC (Phenyl), 367; 12.29 PCH2, 367; 12.30 PCH3, 367; 12.31 PPhenyl, 367; 12.32 P = S, 368; 12.33 PSH, 370; 12.34 PN, 370; 12.35 P = N, 370; 12.36 PF, PCl, PC, 371; 12.37 SH, 371; 12.38 Sulfides and Disulfides, 371; 12.39 CH2S, 372; 12.40 CH3S, 372; 12.41 S-CH = CH2, 372; 12.42 S-Aryl, 373; 12.43 SF, 373; 12.44 SO, 373; 12.45 S0 2 , 373; 12.46 Sulfones, 374; 12.47 Sulfonamides, 375; 12.48 Sulfonic Acids, 375; 12.49 Sulfonic Acid Salts, 375; 12.50 Sulfinic Acids, 375; 12.51 HSO-, 376; 12.52 S042", 376; 12.53 SO/", 376; 12.54 SOCH2, 376; 12.55 Thionylamine, 376; 12.56 C = S, 377; 12.57 (FHF) , 379; 12.58 FCH, 379; 12.59 FC = C, 380; 12.60 FC = 0, 380; 12.61 FAryl, 380; 12.62 CF Stretch, 380; 12.63 CCl, 381; 12.64 CBr, 383; 12.65 CI, 385; 12.66 Aryl Halides, 383; 12.67 Organometallic Compounds, 384; 12.68 Inorganic Metal Oxides, 385

355

Chapter 13 MAJOR SPECTRA-STRUCTURE CORRELATIONS BY SPECTRAL REGIONS

13.1 Introduction, 387; 13.2 3700-3100 cm" (OH, NH, and =CH), 387; 13.3 3100-2980 cm"1 (Aryl, Olefinic, and Three-Membered Ring CH), 388; 13.4 3000-2700 CHT1 (Aliphatic CH), 388; 13.5 3100-2400 cm" (Acidic and Strongly Bonded Hydrogens), 389; 13.6 2600-2100 cm" (SH, BH, PH, and SiH), 389; 13.7 2300-1900 cm" (X=Y andX = Y = Z), 389; 13.8 2000-1700 cm" (Aryl and Olefinic Overtones), 389; 13.9 1900-1550 cm-' (C = 0), 390; 13.10 1700-1550 cm" (C = C and C = N), 390; 13.11 1600-1450 cm-' (N = 0), 390; 13.12 1660-1500 cm 1 (NH2, NH3 + , and CNH), 391; 13.13 1620-1420 ctir' (Aromatic and Heteroaromatic Rings), 391; 13.14 1500-1250 cm" (CH3 and CH2, 391; 13.15 1470-1310 cm"1 ( B O, B-N, NO, , CO, 2 , and NH4 , 391; 13.16 1400-1000 cm"' (S0 2 , S03", SO, and SO,2-), 392; 13.17 1300-1140 cm" (P = 0), 392; 13.18 1350-1120 cm 1 (CF3 and CF2, 392; 13.19 1350-1150 cm" (CH2 and CH Wag), 392; 13.20 1300-1000 cm" (CO), 392; 13.21 1100-830 cm" (SiO and PO), 393; 13.22 1000-600 cm" (Olefinic and Acetylenic CH-Wag), 393; 13.23 900700 cm" (Aromatic CH Wag), 393; 13.24 830-500 cm" (CC1, CBr, and Cl),

387

CONTENTS

393; 13.25 900-500 cm ' (OH, NH, and NH 2 Wag), 393; 13.26 800-200 cm-' (Selected Inorganic Absorptions), 394; 13.27 Mixtures, 394; 13.28 Correlation Charts, 395; 13.29 Selected Infrared Spectra Illustrating Functional Group Frequencies, 398; 13.30 Selected Raman Spectra, 478

Chapter 14 THE THEORETICAL ANALYSIS OF MOLECULAR VIBRATIONS

14.1 Normal Modes of Vibration, 483; 14.2 The Linear Triatomic Model's Stretching Frequencies, 486; 14.3 Internal Coordinates, 490; 14.4 Vibrational Solution Using Internal Coordinates, 491; 14.5 The G Matrix, 493; 14.6 The L Matrix, 497; 14.7 Normal Coordinates, 498; 14.8 Potential Energy Distribution, 500; 14.9 The Form of the Normal Coordinates, 501; 14.10 Symmetry Coordinates, 502; 14.11 The CHC13 Molecule, 505; 14.12 The Internal Coordinates forCHCl 3 , 508; 14.13 The Symmetry Coordinates forCHCl,, 509; 14.14 The G Matrix for CHC13, 518; 14.15 The F Matrix for CHC13, 526; 14.16 The Secular Determinants for CHC13, 528; 14.17 The Frequencies of the CDC13 Molecules, 529; 14.18 Comparison of Experimental and Calculated Wavenumbers, 530; 14.19 The Form of the Chloroform Normal Coordinates, 530; 14.20 The Potential Function Problem, 535; 14.21 A Review of Matrix Notation, 536; 14.22 The Normal Coordinate Problem in Matrix Form, 539

483

INDEX

543