Introduction to Infrared and Raman Spectroscopy

Preface

Chapter I Vibrational and Rotational Spectra


1.1 Introduction


1.2 Photon Energy


1.3 Degrees of Freedom of Molecular Motion


1.4 Normal Modes of Vibration


1.5 Mechanical Molecular Models


1.6 Coordinates Used to Describe Molecular Vibrations


1.7 Classical Vibrational Frequency Formula for Diatomic Molecule


1.8 Infrared Absorption and the Change in Dipole Moment


1.9 Anharmonicity and Overtones


1.10 Vibrational Potential Function


1.11 Introduction to the Quantum Effect


1.12 The Quantum Mechanical Harmonic Oscillator


1.13 The Boltzmann Distribution Function


1.14 Vibrational Transitions and Infrared Absorption


1.15 The Anharmonic Oscillator


1.16 Combination and Difference Bands


1.17 Fermi Resonance


1.18 Rotation of Linear Molecules


1.19 Rotational Transitions and Infrared Absorption


1.20 The Non Rigid Rotator


1.21 Rotational Line Intensities


1.22 Types of Rotators


1.23 Rotation of Symmetric Top Molecules


1.24 Vibrational-Rotational Spectrum, Classical Picture


1.25 Vibrational-Rotational Spectrum, Quantum Mechanical Treatment


1.26 Vibrational-Rotational Spectrum Non Rigid Rotator


1.27 Spherical Top Molecules


1.28 Symmetrical Top Molecules


1.29 Asymmetrical Top Molecules


1.30 The Raman Effect


1.31 Polarizability


1.32 The Tensor Character of the Polarizability


1.33 Depolarization Ratio


1.34 Pure Rotational Raman Spectra

Chapter 2 Experimental Considerations


2.1 Source of Infrared Radiation


2.2 Infrared Monochromators and Filters


2.3 Infrared Detectors


2.4 Commercial Instruments


2.5 Instrument Calibration


2.6 Sample Handling Techniques


2.7 Quantitative Analysis


2.8 Polarized Infrared Radiation


2.9 Infrared Fourier Transform Spectroscopy


2.10 Raman Sources


2.11 Raman Spectrographs


2.12 Raman Measurements

Chapter 3 Molecular Symmetry


3.1 Symmetry Properties


3.2 Point Groups


3.3 Group Theory


3.4 Group Theory Applied to Point Groups


3.5 Representations of Groups


3.6 Irreducible Representations


3.7 The Character Table


3.8 Irreducible Representation Components in a Representation


3.9 Transformation Properties of a Vector


3.10 The Number of Fundamentals of Each Type


3.11 Selection Rules


3.12 Infrared Activity of Fundamentals


3.13 Raman Activity of Fundamentals


3.14 Overtone and Combination Bands


3.15 Symmetry Coordinates


3.16 Isotope Effects and the Product Rule


3.17 Character Tables and Selection Rules

Chapter 4 The Vibrational Origin of Group Frequencies


4.1 Introduction


4.2 Diatomic Oscillators


4.3 Coupled Oscillators


4.4 Unsymmetrical Coupled Oscillators


4.5 X-H Stretching Frequencies


4.6 Triple Bond Vibrations


4.7 Cumulated Double Bonds


4.8 The Linear M1-M2-M3 Model


4.9 X-C ≡ N Compounds


4.10 Carbonyl and C=C Compounds


4.11 Cyclic Compound Stretching Vibrations


4.12 The Bent M1-M2-M1, Stretching Frequencies


4.13 Noncyclic Single Bond Vibrations


4.14 Bend-Bend Interaction


4.15 Bend Stretch Interaction


4.16 Multiple Oscillator Groups


4.17 Interaction Force Constant Effects


4.18 Hydrogen Bonding

Chapter 5 Methyl and Methylene Groups


5.1 Introduction to Group Frequencies


5.2 Methyl Groups


5.3 CH3 Stretching Vibrations


5.4 CH3 Deformation Vibrations


5.5 CH3 Rock Vibrations


5.6 Methylene Groups


5.7 CH2 Stretching Vibrations


5.8 CH2 Deformation Vibrations


5.9 CH2 Wag Vibrations


5.10 CH2 Rock Vibrations


5.11 CH2 Twisting Vibrations


5.12 CH2 in Cyclic Compounds


5.13 Carbon-Hydrogen Group

Chapter 6 Triple Bonds and Cumulated Double Bonds


6.1 Introduction


6.2 Monosubstituted Acetylenes


6.3 Disubstituted Acetylenes


6.4 Aliènes


6.5 Nitriles


6.6 Nitrile N-Oxides and Complexes


6.7 Cyanates


6.8 Isocyanates


6.9 Thiocyanates


6.10 Isothiocyanates


6.11 Nitriles on a Nitrogen Atom


6.12 Carbodiimides


6.13 Ketene Imines


6.14 Diazo Compounds


6.15 Azides


6.16 Aryl Diazonium Salts


6.17 Isocyanides


6.18 Ketenes


6.19 Cyanide Ions


6.20 Cyanate Ions


6.21 Thiocyanate Ions


6.22 Metal Carbonyls


6.23 Three and Four Cumulated Double Bonds

Chapter 7 Olefin Groups


7.1 Non Cyclic Olefins


7.2 Olefinic Hydrogen Wagging Vibrations


7.3 Cyclic C=C

Chapter 8 Aromatic and Heteroaromatic Rings


8.1 Benzene Rings


8.2 The Carbon-Carbon Vibrations


8.3 The 1600cm-1 Region


8.4 The 1500cm-1 Region


8.5 The 700cm-1 Region


8.6 The 900-700cm-1 CH Wag Bands


8.7 The 2000-1650cm-1 Summation Bands


8.8 The 1300-1000cm-1 Region


8.9 The 850-600cm-1 Region


8.10 The 550-400cm-1 Region


8.11 Condensed Ring Aromatic Compounds


8.12 Pyridines


8.13 Pyridine N-Oxides


8.14 Pyrimidines


8.15 Triazines


8.16 Alkyl- or Aryl-Substituted Triazines


8.17 Melamines and Guanamines


8.18 Chloro-, Oxy-, and Thio-substituted Triazines


8.19 Tetrazines


8.20 Heteroaromatic Five-Membered Ring Compounds


8.21 Cyclopentadienyl Ring-Metal Complexes

Chapter 9 Carbonyl Compounds


9.1 Introduction


9.2 Mass Effects


9.3 Bond Angle Effects


9.4 Inductive Effects


9.5 Mesomeric Effects


9.6 Ketones


9.7 α-Chloro Ketones


9.8 Conjugated Ketones


9.9 Conjugated Hydrogen Bonded Ketones


9.10 Bond Angle Effects in Ketones


9.11 Aldehyde CH Vibrations


9.12 Aldehyde Carbonyl Vibrations


9.13 Aldehyde C—C


9.14 Ester C=O


9.15 Ester C—O


9.16 Out-of-Plane Hydrogen Vibrations in Unsaturated Esters


9.17 Groups Next to the Carbonyl in Esters


9.18 Groups on the Oxygen Atoms in Esters


9.19 Lactones


9.20 Thiol Esters and Related Compounds


9.21 Organic Carbonate Derivatives and Related Compounds


9.22 Oxalates


9.23 Anhydrides


9.24 Peroxides, Acyl or Aroyl


9.25 Halogen-Substituted Carbonyls


9.26 Carboxylic Acid OH Stretch


9.27 Carboxyl-Carbonyl Stretch


9.28 Carboxyl OH Bending and C—O Stretching


9.29 Monomeric Acids


9.30 Aliphatic Peroxy Acids


9.31 Aromatic Acids


9.32 Aliphatic Bands in Long Chain n-Aliphatic Carboxylic Acids, Ester, and Soaps


9.33 Carboxyl Salts


9.34 Amino Acids


9.35 Amido Acids


9.36 Unsubstituted Amides


9.37 TV-Substituted Amides (trans)


9.38 N-Substituted Amides (cis) (Lactams)


9.39 Disubstituted Amides


9.40 Ureas


9.41 Carbamates


9.42 Hydroxamic Acids


9.43 Imides


9.44 Isocyanurates


9.45 Acid Hydrazides

Chapter 10 Ethers, Alcohols, and Phenols


10.1 Aliphatic Ethers


10.2 Aromatic Ethers


10.3 Vinyl Ethers


10.4 Cyclic Ether Linkages


10.5 Oxirane Ring Compounds


10.6 OH Stretch in Alcohols and Phenols


10.7 C—O Stretch


10.8 OH Deformation


10.9 Phenols


10.10 Non Cyclic Acetals and Related Compounds


10.11 Cyclic Acetals


10.12 Carbohydrates


10.13 Peroxides

Chapter 11 Amines, C＝N, and N＝O Compounds


11.1 NH2 Stretch in Amines


11.2 NH2 Deformation in Amines


11.3 NH


11.4 C—N in Aliphatic Amines


11.5 C—N in Aromatic Amines


11.6 Aliphatic Bands in Amines


11.7 The Ammonium Ion


11.8 Amine Salts


11.9 C＝N Groups


11.10 Nitro Group


11.11 Organic Nitrates


11.12 Nitramines


11.13 Organic Nitrates


11.14 Inorganic Nitrates and Nitrites


11.15 N＝N Azo


11.16 Azoxy and Azothio Groups


11.17 C-Nitroso Compounds


11.18 Nitrosamines

Chapter 12 Compounds, Containing Boron, Silicon, Phosphorus, Sulfur, or Halogen


12.1 Boron Compounds


12.2 B—O


12.3 B—OH


12.4 B—N


12.5 B—H


12.6 B—Cl


12.7 B—CH3


12.8 B-Phenyl


12.9 Silicon Compounds


12.10 Si—H


12.11 Si—CH3


12.12 Si—CH2—R


12.13 Si—C6H5


12.14 Si—CH＝CH2


12.15 Si—O—R


12.16 Si—O—C6H5


12.17 Si—O—S i


12.18 Si—OH


12.19 Si—Halogen


12.20 Si—N


12.21 Phosphorus Compounds


12.22 P—H


12.23 PO


12.24 P—OH


12.25 P—O—P


12.26 PO2—, POS—, PO32—, PO43—


12.27 P—O—C (Aliphatic)


12.28 P—O—C (Phenyl)


12.29 P—CH2


12.30 P—CH3


12.31 P—Phenyl


12.32 P＝S


12.33 P—SH


12.34 P—N


12.35 P＝N


12.36 P—F, P—Cl, P—C


12.37 S—H


12.38 Sulfides and Disulfides


12.39 CH2—S


12.40 CH3—S


12.41 S—CH＝CH2


12.42 S—Aryl


12.43 S—F


12.44 SO


12.45 SO2


12.46 Sulfones


12.47 Sulfonamides


12.48 Sulfonic Acids


12.49 Sulfonic Acid Salts


12.50 Sulfinic Acids


12.51 HSO4 -


12.52 SO42—


12.53 SO32—


12.54 S—O—CH2


12.55 Thionylamine


12.56 C＝S


12.57 (FHF)-


12.58 FCH


12.59 FC＝C


12.60 FC＝O


12.61 F—Aryl


12.62 CF Stretch


12.63 C—Cl


12.64 C—Br


12.65 C—I


12.66 Aryl Halides


12.67 Organometallic Compounds

Chapter 13 Major Spectra-Structure Correlations by Spectral Regions


13.1 Introduction


13.2 3700-3100cm-1 (OH, NH, and≡CH)


13.3 3100-3000cm-1 (Aryl, Olefinic, and Three-Membered Ring CH)


13.4 3000-2700cm-1' (Aliphatic CH)


13.5 3100-2400cm-1 (Acidic and Strongly Bonded Hydrogens)


13.6 2600-2100cm-1 (SH,BH,PH,and SiH)


13.7 2300-1900cm-1 (X＝Y and X＝Y＝Z)


13.8 2000-1700cm-1 (Aryl and Olefinic Overtones)


13.9 1900-1550cm-1 (C＝O)


13.10 1700-1550cm-1(C＝C and C=N)


13.11 600-1450cm-1 (N＝O)


13.12 1660-1500cm-1 (NH2, NH3+, and CNH)


13.13 1620-1420cm-1(Aromatic and Heteroaromatic Rings)


13.14 1500-1250cm-1 (CH3 and CH2)


13.15 1470-1310cm-1 (B—O, B—N, NO3-, CO32-, and NH4-)


13.16 1400-1000cm-1 (SO2, SO3-, SO, and SO42-)


13.17 1300-1140cm-1 (P＝O)


13.18 1350-1120cm-1 ( CF3 and CF2 )


13.19 1350-1150cm-1( CH2 and CH Wag)


13.20 1300-1000cm-1 (C—O)


13.21 1100-830cm-1 (Si—O and P—O)


13.22 1000-600cm-1 (Olefinic CH Wag)


13.23 900-700cm-1 (Aromatic CH Wag)


13.24 830-500cm-1 (CCI, CBr, snd Cl)


13.25 Near Infrared Region Correlation Chart


13.26 Carbon-Hydrogen Stretching Region Correlation Chart


13.27 Sodium Chloride Region Correlation Charts


13.28 Low Frequency Infrared Region


13.29 Selected Infrared Spectra Illustrating Functional Group Frequencies


13.30 Selected Raman Spectra

Chapter 14 The Theoretical Analysis of Molecular Vibrations


14.1 Normal Modes of Vibration


14.2 The Linear Triatomic Model's Stretching Frequencies


14.3 Internal Coordinates


14.4 Vibrational Solution Using Internal Coordinates


14.5 The G Matrix


14.6 The L Matrix


14.7 Normal Coordinates


14.8 Potential Energy Distribution


14.9 The Form of the Normal Coordinates


14.10 Symmetry Coordinates


14.11 The CHCI3 Molecule


14.12 The Internal Coordinates for CHCI3


14.13 The Symmetry Coordinates for CHCI3


14.14 The G Matrix for CHCI3


14.15 The F Matrix for CHCI3


14.16 The Secular Determinants for CHCI3


14.17 The Frequencies of the CDCI3 Molecules


14.18 Comparison of Experimental and Calculated Wavenumbers


14.19 The Form of the Chloroform Normal Coordinates


14.20 The Potential Function Problem


14.21 A Review of Matrix Notation


14.22 The Normal Coordinate Problem in Matrix Form

Index