Spectroscopy

Cover
Half Title
Title Page
Copyright Page
Table of Contents
Preface
Chapter 1: Introduction to Spectroscopy
1.1: Introduction
1.2: Interaction of Electromagnetic Radiation with Matter
1.2.1: Wave Properties of Electromagnetic Radiation
1.3: Electromagnetic Spectral Range
1.3.1: Radiofrequency Region
1.3.1.1: Microwave region
1.3.1.2: Infrared region
1.3.1.3: Visible and ultraviolet region
1.3.1.4: X-ray region
1.3.1.5: γ-ray region
1.4: Born–Oppenheimer Approximation
1.5: Energy Levels in Molecules and Quantization of Energy
1.6: Mechanism of Absorption and Emission
1.7: Transition Probability and Selection Rule
1.7.1: Transition Moment and Transition Moment Integral
1.7.2: Electronic Selection Rules
1.7.3: Vibrational Selection Rules
1.7.4: Rotational Selection Rules
1.8: Line Width and Line Shapes
1.8.1: Spectral Line Broadening and Line Shapes
1.8.2: Local Effects Broadening
1.8.3: Natural Line Broadening
1.8.4: Doppler Broadening
1.8.5: Pressure (Collision Broadening)
1.8.6: Broadening due to Inhomogeneous Local Effects
1.8.7: Broadening due to Non-local Effects
1.9: Fourier Transform
Chapter 2: Nuclear Magnetic Resonance Spectroscopy
2.1: Introduction
2.2: Nature of Spinning Nucleus
2.3: Effect on the Nucleus of an External Magnetic Field
2.4: Precessional Motion of Nucleus
2.5: Precessional Frequency: Larmor Frequency
2.6: Energy Transitions and the Origin of NMR
2.7: Theory of NMR
2.7.1: Nuclear Spin and Magnetic Moment and Interaction Between Nuclear Spin and Magnetic Field
2.7.2: Population of Nuclear Energy Levels
2.7.3: Saturation and Relaxation
2.8: Concept of Chemical Shift
2.9: Types of Shielding
2.10: Factors Affecting Chemical Shift
2.10.1: Effect of Electronegativity (Inductive Effect)
2.10.2: Van der Waal’s Deshielding
2.10.3: Magnetic Anisotropy
2.10.3.1: Alkenes
2.10.3.2: Alkynes
2.10.3.3: Carbonyl compounds
2.10.3.4: Aromatic compounds
2.10.3.5: Effect of hydrogen bonding
2.10.3.6: Effect of solvents (types, concentration, temperature, and hydrogen bonding)
2.10.3.7: Solvents used in NMR
2.11: Spin–Spin Coupling
2.11.1: The Splitting of Signals in Proton NMR Spectra
2.11.2: Theory of Spin–Spin Coupling
2.12: The General Rule of Spin–Spin Splitting: The (n + 1) Splitting Rule
2.13: Complex NMR Spectra: Breakdown of (n + 1) Splitting Rule
2.13.1: Multiplicative Splitting
2.13.2: Non-first-order Spectra: Breakdown of the (n + 1) Rule
2.14: The Coupling Constant (J)
2.14.1: Factors Influencing Coupling Constant, J, and Various Types of Couplings
2.14.1.1: Geminal coupling
2.14.1.2: Vicinal coupling
2.14.1.3: Long-range proton–proton coupling
2.14.1.4: Heteronuclear coupling
2.14.1.5: 1H–13C spin–spin coupling
2.14.1.6: Deuterium coupling
2.15: Proton Exchange Reaction in NMR Spectrum of Alcohol
2.16: Restricted Rotation
2.17: Deuterium Exchange in NMR Spectroscopy
2.18: Simplification of Complexities of Proton NMR Spectra
2.18.1: By Increase in the Field Strength
2.18.2: By Spin Decoupling Method
2.18.3: By Using Chemical Shift Reagents
2.18.4: NMR of Nuclei Other Than Protons
2.18.4.1: 13C NMR
2.18.4.2: 19F NMR spectroscopy
2.18.4.3: 31P NMR
2.19: Instrumentation of NMR Spectroscopy
2.20: Nuclear Overhauser Effect
2.21: FT-NMR
Chapter 3: Carbon-13: NMR
3.1: Introduction
3.2: Comparison with 1H NMR Spectroscopy
3.2.1: Characteristic Features of 13C NMR Spectra
3.2.2: Referencing 13C NMR Spectra
3.3: Instrumentation
3.4: Interpretation of 13C Spectra
3.4.1: Broadband Decoupling
3.4.2: Off-Resonance Decoupling
3.5: Chemical Shift
3.5.1: Origin
3.5.2: Scale
3.5.3: Effects on sp3: Carbons
3.5.4: α-Substituent Effects
3.5.5: Heavy-Atom α-Effect
3.5.6: α-Effect of Triple Bonds
3.5.7: α-Effect of Double Bonds
3.5.8: β-Substituent Effects
3.5.9: γ-Substituent Effects
3.5.10: δ-Substituent Effects
3.5.11: Membered Rings
3.5.12: Effects on sp2: and sp Carbons
3.5.13: Conjugation with π-Acceptors and π-Donors
3.5.14: Strongly Charged Systems
3.5.15: Carbonyl Groups
3.5.16: Conjugation Effects
3.5.17: Hydrogen Bond Effects
3.6: Application of 13C NMR
3.6.1: Identification of Molecules
3.6.2: Soil Organic Matter Studies
3.6.3: Physical Separations and Structural Characterization of Organic C in Bulk Soils
Chapter 4: Electron Spin Resonance Spectroscopy
4.1: Introduction
4.2: Basic Principles and Origin of ESR Spectra
4.3: The Electron g-Factor
4.3.1: Factor Affecting g-Factor
4.3.2: Determination of g-Values
4.4: Saturation and Relaxation in ESR Spectroscopy
4.4.1: Spin–Lattice Relaxation Process
4.4.2: Spin–Spin Relaxation Process
4.5: Splitting of ESR Signals: Hyperfine Interaction
4.6: Zero-Field Splitting: Kramer Degeneracy
4.7: Isotropic Coupling Constant
4.7.1: Isotropic Hyperfine Splitting from Single Set of Equivalent Protons
4.7.2: Isotropic Hyperfine Splitting from Multiple Set of Equivalent Protons
4.8: Anisotropy and Hyperfine Splitting
4.8.1: Anisotropy in Crystals
4.8.1.1: Cubic system
4.8.1.2: Uniaxial symmetry
4.8.1.3: Rhombic symmetry
4.9: Instrumentation
4.9.1: Source
4.9.1.1: Microwave oscillator
4.9.1.2: Wave guide and wave meter
4.9.1.3: Attenuator
4.9.1.4: Isolator
4.9.2: Sample Cell/Cavity
4.9.3: A Magnet System
4.9.4: Detector
4.9.5: Recorder
4.9.5.1: Working of instrument
4.10: Application of ESR Spectroscopy
Chapter 5: Infrared Spectroscopy
5.1: Introduction
5.2: Principle of Infrared Spectroscopy
5.3: The Vibration in a Diatomic Molecule
5.3.1: Zero-Point Energy
5.3.2: Infrared Spectra and Selection Rule
5.3.3: Limitations and Drawbacks of Simple Harmonic Oscillator Model
5.4: The Diatomic Molecules as Anharmonic Oscillator
5.4.1: Zero-Point Energy for Anharmonic Oscillator
5.4.2: Infrared Spectra and the Selection Rule
5.4.3: Hot Bands
5.5: The Vibrating Rotating Diatomic Molecule (Vibrational–Rotational Spectra)
5.5.1: Energy Levels of Rotating Vibrators
5.5.1.1: Case I: Diatomic molecules performing harmonic oscillations and behaving as a rigid rotator
5.5.1.2: Case II: Diatomic molecules performing anharmonic oscillation and behaving as non-rigid rotators
5.6: Vibration and Rotation Spectra of Polyatomic Molecule
5.6.1: Number of Fundamental Vibrations and Their Symmetry in a Polyatomic Molecule
5.6.1.1: Normal modes of vibrations in polyatomic molecules
5.6.2: The Influence of Rotation on the Spectra of Polyatomic Molecules
5.6.2.1: Linear molecules with parallel vibrations
5.6.2.2: Linear molecules with perpendicular vibrations
5.6.2.3: Symmetric top molecules with parallel vibrations
5.6.2.4: Symmetric top molecules with perpendicular vibrations
5.7: Factor Affecting the Infrared Absorption
5.7.1: Effect of Force Constant, Bond Strength, and Isotopic Substitution
5.7.2: Electronic Effects
5.7.2.1: Mesomeric effect
5.7.2.2: Inductive effect
5.7.3: Bond Angles Effect
5.7.4: Effect of Hydrogen Bonding
5.7.4.1: Intramolecular hydrogen bonding
5.8: Application and Analysis by Infrared Spectra
5.8.1: Structural Analysis
5.9: The Infrared Spectrometer: Instrumentation and Technique
5.9.1: Infrared Light Sources
5.9.2: Monochromator
5.9.3: Detectors
5.9.4: Dispersive IR Spectrometer
5.10: Drawback of Double Beam Dispersive Spectrometer
5.11: Fourier Transform Infrared Spectrometer
5.11.1: Basic Principle and Operation of FTIR Fourier Transform Infrared Spectroscopy
5.11.2: Advantages of FTIR
Chapter 6: Microwave Spectroscopy
6.1: Introduction
6.2: Rotational Spectra of Linear Diatomic Molecule
6.2.1: The Rigid Linear Diatomic Molecule
6.2.2: Description of Rotational Spectra of Rigid Rotating Diatomic Molecule
6.3: Various Transitions in the Rotational Spectrum
6.4: The Selection Rule
6.5: Intensities of Rotational Spectral Lines
6.6: Isotopic Substitution
6.7: Techniques and Instrumentation
6.7.1: The Source and Monochromator
6.7.2: Waveguide
6.7.3: Sample and Sample Space
6.7.4: Detector
6.7.5: Spectrum Recorder
6.8: Applications of Microwave Spectroscopy
Chapter 7: Raman Spectroscopy
7.1: Introduction
7.2: Quantum Mechanical Concept of Raman Effect
7.3: Molecular Polarizability and the Raman Effect
7.4: Rotational Raman Spectra
7.5: Vibrational Raman Spectra
7.6: Rotational–Vibrational Raman Spectra
7.7: Instrumentation
7.7.1: Light (Radiation Source)
7.7.2: A Sample Illumination and Light Collection Optic System
7.7.3: Detectors and Data Recording System
7.8: Comparison Between IR and Raman Spectroscopic Techniques
Chapter 8: Electronic Spectroscopy
8.1: Introduction
8.2: The Nature of Electronic Excitations
8.2.1: σ → σ* Electronic Transition
8.2.2: n → σ* Electronic Transition
8.2.3: п → п * Transition
8.2.4: n → п* Transition
8.3: Selection Rule for the Electronic Transition
8.4: Beer–Lambert Law
8.5: Chromophore and Auxochrome
8.6: Effect of Solvent on Electronic Transition (Solvent Effect)
8.7: Effect of Conjugation
8.8: Woodward–Fisher Rule
8.8.1: For Dienes
8.8.2: For Carbonyl Compounds: Enones
8.8.3: Woodward Rule for Enone System
8.8.4: Woodward’s Rule for α, β-Unsaturated Aldehydes, Acids, and Esters
8.9: Absorption in Aromatic Compounds
8.10: Color in Transition Metal Complex
8.11: Charge Transfer Transition
8.11.1: Ligand to Metal Charge Transfer
8.11.2: Metal to Ligand Charge Transfer
Chapter 9: Fluorescence and Phosphorescence Spectroscopy
9.1: Introduction
9.2: Principle of Fluorescence and Phosphorescence
9.2.1: Rules Governing Fluorescence
9.2.1.1: Kasha’s rule
9.2.1.2: Frank–Condon (FC) principle
9.3: Instrumentation
9.4: General Properties of Fluorescence and Phosphorescence
9.4.1: Fluorescence
9.4.2: Phosphorescence
9.5: Fluorescence Parameters
9.5.1: Fluorescence Emission Spectra (λex: Fixed)
9.5.1.1: Stokes’s shift
9.6: Fluorescence Excitation Spectra [Wavelength of Emission (λem): Fixed]
9.7: Fluorescence Quantum Yield
9.8: Fluorescence Lifetime
9.9: Synchronous Fluorescence Spectroscopy
9.10: Fluorescence and Structure
9.11: Fluorescence and Temperature
9.12: Intrinsic and Extrinsic Fluorophores
9.13: Applications
9.14: Fluorophores: Intrinsic
9.14.1: Concentration Determination
9.14.2: Study of Excited State Properties
9.14.3: Excited State Acidity Constants
9.14.3.1: Forster cycle method: Theoretical
9.14.3.2: Fluorimetric titration method (pH dependence of fluorescence
9.15: Solvotochromic Shifts
9.16: Fluorescence Quenching
9.17: Synchronous Fluorescence Spectroscopy Applications
9.18: Phosphorescence Spectroscopy
9.19: Conclusions
Chapter 10: X-ray Fluorescence and Its Applications for Materials Characterization
10.1: Introduction
10.2: Production of X-rays
10.3: Interaction of X-rays with Matter
10.4: Characteristic X-rays
10.5: X-ray Fluorescence Principle
10.5.1: X-ray Fluorescence Analysis
10.6: Instrumentation and Geometrical Consideration
10.7: Application of XRF in Materials Characterization
10.7.1: Some Examples of XRF Application in Different Areas of Science and Technology
10.8: Advancements in XRF Analysis
Index