Introduction to Infrared and Raman Spectroscopy focuses on the theoretical and experimental aspects of infrared and Raman spectroscopy, with emphasis on detailed group frequency correlations and their vibrational origin. Topics covered include vibrational and rotational spectra, molecular symmetry, methyl and methylene groups, triple bonds and cumulated double bonds, and olefin groups. Aromatic and heteroaromatic rings are also considered, along with carbonyl compounds and molecular vibrations. This book is comprised of 14 chapters and begins with a discussion on the use of Raman and infrared spectroscopy to study the vibrational and rotational frequencies of molecules, paying particular attention to photon energy and degrees of freedom of molecular motion. The quantum mechanical harmonic oscillator and the anharmonic oscillator are described. The next chapter focuses on the experimental techniques and instrumentation needed to measure infrared absorption spectra and Raman spectra. Symmetry is then discussed from the standpoint of the spectroscopist. The following chapters explore the vibrational origin of group frequencies, with an emphasis on mechanical effects; spectra-structure correlations; and the spectra of compounds such as ethers, alcohols, and phenols. The final chapter demonstrates how the frequencies and forms of a nonlinear molecule's normal modes of vibration may be calculated mathematically. This monograph will be a useful resource for spectroscopists and physical scientists.
Inhalt
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