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Modern Spectroscopy by J Michael Hollas

Modern Spectroscopy by J Michael Hollas

Modern Spectroscopy by J. Michael Hollas

Free Download Modern Spectroscopy by J Michael Hollas – 4th Edition

Modern Spectroscopy by J Michael Hollas

Authors:
J. Michael Hollas
University of Reading

 

Table of Contents

Preface to first edition xiii

Preface to second edition xv

Preface to third edition xvii

Preface to fourth edition xix

Units, dimensions, and conventions xxi

Fundamental constants xxiii

Useful conversion factors xxv

1 Some important results in quantum mechanics

1.1 Spectroscopy and quantum mechanics

1.2 The evolution of quantum theory

1.3 The Schro¨dinger equation and some of its solutions

1.3.1 The Schro¨dinger equation

1.3.2 The hydrogen atom

1.3.3 Electron spin and nuclear spin angular momentum

1.3.4 The Born–Oppenheimer approximation

1.3.5 The rigid rotor

1.3.6 The harmonic oscillator

Modern Spectroscopy by J Michael Hollas

2 Electromagnetic radiation and its interaction with atoms and molecules

2.1 Electromagnetic radiation

2.2 Absorption and emission of radiation

2.3 Line width

2.3.1 Natural line broadening

2.3.2 Doppler broadening

2.3.3 Pressure broadening

2.3.4 Power, or saturation, broadening

2.3.5 Removal of line broadening

2.3.5.1 Effusive atomic or molecular beams

2.3.5.2 Lamb dip spectroscopy

Modern Spectroscopy by J Michael Hollas

3 General features of experimental methods

3.1 The electromagnetic spectrum

3.2 General components of an absorption experiment

3.3 Dispersing elements

3.3.1 Prisms

3.3.2 Diffraction gratings

3.3.3 Fourier transformation and interferometers

3.3.3.1 Radiofrequency radiation

3.3.3.2 Infrared, visible and ultraviolet radiation

3.4 Components of absorption experiments in various regions of the spectrum

3.4.1 Microwave and millimeter-wave

3.4.2 Far-infrared

3.4.3 Near-infrared and mid-infrared

3.4.4 Visible and near-ultraviolet

3.4.5 Vacuum- or far-ultraviolet

3.5 Other experimental techniques

3.5.1 Attenuated total reflectance spectroscopy and reflection–absorption infrared spectroscopy

3.5.2 Atomic absorption spectroscopy

3.5.3 Inductively coupled plasma atomic emission spectroscopy

3.5.4 Flash photolysis

3.6 Typical recording spectrophotometers for the near-infrared, mid-infrared, visible and near-ultraviolet regions

4 Molecular symmetry

4.1 Elements of symmetry

4.1.1 n-Fold axis of symmetry, Cn

4.1.2 Plane of symmetry, s

4.1.3 Centre of inversion, i

4.1.4 n-Fold rotation–reflection axis of symmetry, Sn

4.1.5 The identity element of symmetry, I (or E)

4.1.6 Generation of elements

4.1.7 Symmetry conditions for molecular chirality

4.2 Point groups

4.2.1 Cn point groups

4.2.2 Sn point groups

4.2.3 Cnv point groups

4.2.4 Dn point groups

4.2.5 Cnh point groups

4.2.6 Dnd point groups

4.2.7 Dnh point groups

4.2.8 Td point group

4.2.9 Oh point group

4.2.10 Kh point group

4.2.11 Ih point group

4.2.12 Other point groups

4.3 Point group character tables

4.3.1 C2v character table

4.3.2 C3v character table

4.3.3 C1v character table

4.3.4 Ih character table

4.4 Symmetry and dipole moments

5 Rotational spectroscopy

5.1 Linear, symmetric rotor, spherical rotor, and asymmetric rotor molecules

5.2 Rotational infrared, millimeter-wave, and microwave spectra

5.2.1 Diatomic and linear polyatomic molecules

5.2.1.1 Transition frequencies or wavenumbers

5.2.1.2 Intensities

5.2.1.3 Centrifugal distortion

5.2.1.4 Diatomic molecules in excited vibrational states

5.2.2 Symmetric rotor molecules

5.2.3 Stark effect in diatomic, linear, and symmetric rotor molecules

5.2.4 Asymmetric rotor molecules

5.2.5 Spherical rotor molecules

5.2.6 Interstellar molecules detected by their radiofrequency, microwave or millimeter-wave spectra

5.3 Rotational Raman spectroscopy

5.3.1 Experimental methods

5.3.2 Theory of rotational Raman scattering

5.3.3 Rotational Raman spectra of diatomic and linear polyatomic molecules

5.3.4 Nuclear spin statistical weights

5.3.5 Rotational Raman spectra of symmetric and asymmetric rotor molecules

5.4 Structure determination from rotational constants

Modern Spectroscopy by J Michael Hollas

6 Vibrational spectroscopy

6.1 Diatomic molecules

6.1.1 Infrared spectra

6.1.2 Raman spectra

6.1.3 Anharmonicity

6.1.3.1 Electrical anharmonicity

6.1.3.2 Mechanical anharmonicity

6.1.4 Vibration–rotation spectroscopy

6.1.4.1 Infrared spectra

6.1.4.2 Raman spectra

6.2 Polyatomic molecules

6.2.1 Group vibrations

6.2.2 Number of normal vibrations of each symmetry species

6.2.2.1 Non-degenerate vibrations

6.2.2.2 Degenerate vibrations

6.2.3 Vibrational selection rules

6.2.3.1 Infrared spectra

6.2.3.2 Raman spectra

6.2.4 Vibration–rotation spectroscopy

6.2.4.1 Infrared spectra of linear molecules

6.2.4.2 Infrared spectra of symmetric rotors

6.2.4.3 Infrared spectra of spherical rotors

6.2.4.4 Infrared spectra of asymmetric rotors

6.2.5 Anharmonicity

6.2.5.1 Potential energy surfaces

6.2.5.2 Vibrational term values

6.2.5.3 Local mode treatment of vibrations

6.2.5.4 Vibrational potential functions with more than one minimum

6.2.5.4(a) Inversion vibrations

6.2.5.4(b) Ring-puckering vibrations

6.2.5.4(c) Torsional vibrations

7 Electronic spectroscopy

7.1 Atomic spectroscopy

7.1.1 The periodic table

7.1.2 Vector representation of momenta and vector coupling approximations

7.1.2.1 Angular momenta and magnetic moments

7.1.2.2 Coupling of angular momenta

7.1.2.3 Russell–Saunders coupling approximation

7.1.2.3(a) Non-equivalent electrons

7.1.2.3(b) Equivalent electrons

7.1.3 Spectra of alkali-metal atoms

7.1.4 Spectrum of the hydrogen atom

7.1.5 Spectra of helium and the alkaline earth metal atoms

7.1.6 Spectra of other polyelectronic atoms

7.2 Electronic spectroscopy of diatomic molecules

7.2.1 Molecular orbitals

7.2.1.1 Homonuclear diatomic molecules

7.2.1.2 Heteronuclear diatomic molecules

7.2.2 Classification of electronic states

7.2.3 Electronic selection rules

7.2.4 Derivation of states arising from configurations

7.2.5 Vibrational coarse structure

7.2.5.1 Potential energy curves in excited electronic states

7.2.5.2 Progressions and sequences

7.2.5.3 The Franck–Condon principle

7.2.5.4 Deslandres tables

7.2.5.5 Dissociation energies

7.2.5.6 Repulsive states and continuous spectra

7.2.6 Rotational fine structure

7.2.6.1 1S71S electronic and vibronic transitions

7.2.6.2 1P71S electronic and vibronic transitions

7.3 Electronic spectroscopy of polyatomic molecules

7.3.1 Molecular orbitals and electronic states

7.3.1.1 AH2 molecules

7.3.1.1(a) ffHAH¼180_

7.3.1.1(b) ffHAH¼90_

7.3.1.2 Formaldehyde (H2CO)

7.3.1.3 Benzene

7.3.1.4 Crystal field and ligand field molecular orbitals

7.3.1.4(a) Crystal field theory

7.3.1.4(b) Ligand field theory

7.3.1.4(c) Electronic transitions

7.3.2 Electronic and vibronic selection rules

7.3.3 Chromophores

7.3.4 Vibrational coarse structure

7.3.4.1 Sequences

7.3.4.2 Progressions

7.3.4.2(a) Totally symmetric vibrations

7.3.4.2(b) Non-totally symmetric vibrations

7.3.5 Rotational fine structure

7.3.6 Diffuse spectra

8 Photoelectron and related spectroscopies

8.1 Photoelectron spectroscopy

8.1.1 Experimental methods

8.1.1.1 Sources of monochromatic ionizing radiation

8.1.1.2 Electron velocity analyzers

8.1.1.3 Electron detectors

8.1.1.4 Resolution

8.1.2 Ionization processes and Koopmans’ theorem

8.1.3 Photoelectron spectra and their interpretation

8.1.3.1 Ultraviolet photoelectron spectra of atoms

8.1.3.2 Ultraviolet photoelectron spectra of molecules

8.1.3.2(a) Hydrogen

8.1.3.2(b) Nitrogen

8.1.3.2(c) Hydrogen bromide

8.1.3.2(d) Water

8.1.3.2(e) Benzene

8.1.3.3 X-ray photoelectron spectra of gases

8.1.3.4 X-ray photoelectron spectra of solids

8.2 Auger electron and X-ray fluorescence spectroscopy

8.2.1 Auger electron spectroscopy

8.2.1.1 Experimental method

8.2.1.2 Processes in Auger electron ejection

8.2.1.3 Examples of Auger electron spectra

8.2.2 X-ray fluorescence spectroscopy

8.2.2.1 Experimental method

8.2.2.2 Processes in X-ray fluorescence

8.2.2.3 Examples of X-ray fluorescence spectra

8.3 Extended X-ray absorption fine structure

Modern Spectroscopy by J Michael Hollas

9 Lasers and laser spectroscopy

9.1 General discussion of lasers

9.1.1 General features and properties

9.1.2 Methods of obtaining the population inversion

9.1.3 Laser cavity modes

9.1.4 Q-switching

9.1.5 Mode locking

9.1.6 Harmonic generation

9.2 Examples of lasers

9.2.1 The ruby and alexandrite lasers

9.2.2 The titanium–sapphire laser

9.2.3 The neodymium–YAG laser

9.2.4 The diode or semiconductor laser

9.2.5 The helium-neon laser

9.2.6 The argon-ion and krypton ion lasers

9.2.7 The nitrogen (N2) laser

9.2.8 The excimer and exciplex lasers

9.2.9 The carbon dioxide laser

9.2.10 The dye lasers

9.2.11 Laser materials in general

9.3 Uses of lasers in spectroscopy

9.3.1 Hyper Raman spectroscopy

9.3.2 Stimulated Raman spectroscopy

9.3.3 Coherent anti-Stokes Raman scattering spectroscopy

9.3.4 Laser Stark (or laser electron resonance) spectroscopy

9.3.5 Two-photon and multiphoton absorption

9.3.6 Multiphoton dissociation and laser separation of isotopes

9.3.7 Single vibronic level, or dispersed, fluorescence

9.3.8 Light detection and ranging (LIDAR)

9.3.9 Cavity ring-down spectroscopy

9.3.10 Femtosecond spectroscopy

9.3.11 Spectroscopy of molecules in supersonic jets

9.3.11.1 Properties of a supersonic jet

9.3.11.2 Fluorescence excitation spectroscopy

9.3.11.3 Single vibronic level, or dispersed, fluorescence spectroscopy

9.3.11.4 Zero kinetic energy photoelectron spectroscopy

Exercises

Bibliography

Appendix

A Character tables

B Symmetry species of vibrations

Index of Atoms and Molecules

Subject Index

 

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