Atomic and molecular spectroscopy: basic concepts and applications
"Elucidates various spectroscopic techniques including atomic spectroscopy, pure rotational spectroscopy, vibrational spectroscopy of diatomic and polyatomic molecules, Raman spectroscopy and electronic spectroscopy"--
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Delhi
Cambridge Univ. Press
2015
|
| Schlagworte: | |
| Online-Zugang: | Klappentext Inhaltsverzeichnis |
| Zusammenfassung: | "Elucidates various spectroscopic techniques including atomic spectroscopy, pure rotational spectroscopy, vibrational spectroscopy of diatomic and polyatomic molecules, Raman spectroscopy and electronic spectroscopy"-- |
| Beschreibung: | Includes bibliographical references and index |
| Beschreibung: | XX, 415 S. Ill., graph. Darst. |
| ISBN: | 9781107063884 |
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Datensatz im Suchindex
| _version_ | 1804152777960587264 |
|---|---|
| adam_text | This book is intended for under-
graduate and graduate students of
physical sciences for a course on
atomic and molecular spectroscopy.
It aims to help students understand
the essential concepts of different
spectroscopic techniques in a simple
and clear manner. Beginning with
the fundamental concepts of
spectroscopy including properties
of waves, electromagnetic radiation,
Boltzmanns population distribution,
line broadening and Lambert-Beers
law, it then goes on to the postulates
of quantum mechanics which are
necessary to understand the time-
dependent perturbation theory. The
book also encompasses various
spectroscopic techniques including
atomic spectroscopy, pure rotational
spectroscopy, vibrational
spectroscopy of diatomic and
polyatomic molecules, Raman
spectroscopy and electronic
spectroscopy. Solved and unsolved
exercises are provided throughout
the book for easy understanding and
better assessment.
Rita Kakkar, FRSC, is Professor at
the Department of Chemistry,
University of Delhi. She has been
teaching quantum mechanics,
spectroscopy and computational
chemistry in this department for over
30 years. Kakkar s areas of research
include computational chemistry
applied to problems in the life
sciences and nanosciences, as well as
computational spectroscopy. She is a
life member of Chemical Research
Society of India (CRSI) and is a
member of the American Chemical
Society (ACS). She is a Fellow of the
Royal Society of Chemistry, London.
Spectroscopy is the study of electromagnetic radiation and its interaction with
solid, liquid, gas and plasma. It is one of the widely used analytical techniques to
study the structure of atoms and molecules. The technique is also employed to
obtain information about atoms and molecules as a result of their distinctive
spectra. The fast spreading field of spectroscopic applications has made
noteworthy influence on many disciplines including energy research, chemical
processing, environmental protection and medicine.
This book aims to introduce students to the topic of spectroscopy. The author
has avoided mathematical aspects of the subject as far as possible,· they appear in
the text only when inevitable. The mathematical examples have been kept at a
level that does not require in-depth knowledge of mathematics. Including the
topics such as time-dependent perturbation theory, laser action and applications
of Group Theory in interpretation of spectra, the book offers a detailed coverage
of the basic concepts and applications of spectroscopy.
Key Features
■ Atomic Spectroscopy.· Detailed simplified discussion on the Russell—Saunders
and jj-coupling schemes
■ Rotational Spectroscopy·. Explanation of Stark effect and its applications
■ Vibrational Spectroscopy·. Simple discussion on pure vibrational spectroscopy
of diatomics, influence of rotational lines and nuclear spin effect
■ Raman Spectroscopy.· Combined use of 1R and Raman spectra in structure
determination with examples
■ Electronic Spectroscopy: Detailed discussion on diatomics and polyatomics,
giving the kind of transitions and how they can be recognized
Rita Kakkar, FRSC, is Professorat the Department of Chemistry, University
of Delhi. She has been teaching quantum mechanics, spectroscopy and
computational chemistry in this department for over 30 years and is also
involved in developing e-content and delivering online lectures on various
topics of physical chemistry.
Contents
a
List of Figures
List of Tables XV
Preface
Acknowledgements
List of Abbreviations xxi
1 Fundamentals of Spectroscopy 1
1.1 Introduction 1
1.2 Some Properties of Waves 2
1.2.1 Travelling waves 5
1.3 Electromagnetic Radiation 6
1.3.1 Wave nature of light 6
1.3.2 Particulate nature of radiation 8
1.4 Electromagnetic Spectrum 12
1.5 Blackbody Radiation 13
1.6 Boltzmann’s Population Distribution 15
1.7 Einstein’s Coefficients 18
1.7.1 Lasers 22
1.8 Line Broadening 24
1.8.1 Natural line broadening 24
1.8.2 Pressure or collisional broadening 32
1.8.3 Doppler broadening 32
1.9 Lambert-Beer’s Law 38
1.9.1 Power or saturation broadening 41
1.10 Fourier Transform Spectroscopy 42
1.11 Summary 46
1.12 Exercises 47
2 Theoretical Principles 51
2.1 Introduction 51
2.2 The Postulates of Quantum Mechanics Explained 52
vl Contents
2.3 Time-Dependent Perturbation 57
2.3.1 The interaction of electromagnetic radiation with a molecular system 60
2.4 Einstein’s Coefficient of Induced Absorption 65
2.4.1 Comparison with experimental quantities 68
2.5 Einstein’s Coefficients of Induced and Spontaneous Emission 70
2.6 The Basis of Selection Rules 72
2.7 Overview of Selection Rules 74
2.8 Summary 77
2.9 Exercises 77
3 Atomic Spectroscopy 79
3.1 Introduction 79
3.2 The Bohr Theory of the Hydrogen Atom 79
3.3 Hydrogen and Hydrogen-like Ion Spectra 83
3.3.1 Transition probabilities 86
3.4 Multi-Electron Atoms 89
3.4.1 Alkali metal spectra 90
3.4.2 Two-electron systems 92
3.4.3 Ground state terms 102
3.4.4 Quantitative treatment of the coupling of orbital and spin
angular momenta for multi-electron atoms 103
3.4.5 Intermediate coupling 109
3.4.6 Interaction with external fields 109
3.5 Photoelectron Spectroscopy 115
3.6 Summary 117
3.7 Exercises 118
4 Pure Rotational Spectroscopy 124
4.1 Overview of Molecular Spectra 124
4.2 The Rigid Diatomic Molecule (The Rigid Rotor) 127
4.2.1 Interaction of radiation with a rotating molecule 134
4.2.2 Rotational spectra and bond lengths of diatomic molecules 137
4.2.3 The effect of isotopic substitution 139
4.2.4 Rotational energy level populations: Intensities of spectral lines 141
4.2.5 Centrifugal distortion 147
4.3 Rotation of Polyatomic Molecules: Classification of Molecules 149
4.3.1 Linear molecules 152
4.3.2 Spherical tops 156
4.3.3 Symmetric tops 156
4.3.4 Asymmetric top molecules 165
4.4 The Effect of Electric Fields: The Stark Effect 169
4.4.1 Effect on the energy levels of a symmetric top 169
4.4.2 Stark effect for linear molecules 172
Contents vii
4.5 Applications of Microwave Spectroscopy 172
4.6 Summary 173
4.7 Exercises 174
5 Vibrational Spectroscopy of Diatomics 182
5.1 Introduction 182
5.2 Oscillations of Systems with One Degree of Freedom 182
5.3 The Diatomic Molecule 185
5.3.1 Lagrange’s equations of motion 187
5.3.2 Normal coordinates and linear transformations 188
5.3.3 Simultaneous diagonalization 189
5.3.4 Heteronuclear diatomic molecules 191
5.3.5 Mass-weighted coordinates 192
5.4 Quantum Mechanical Treatment 196
5.4.1 Mechanism of infrared radiation absorption: qualitative ideas 201
5.4.2 Quantitative treatment of selection rules 202
5.5 The Potential Energy Function for a Chemical Bond 208
5.5.1 Experimental accuracy of the Morse potential 214
5.5.2 Force constants 214
5.5.3 Isotopic substitution 216
5.5.4 Vibrational dependences of rotational constants 221
5.5.5 Combination differences 223
5.6 Summary 224
5.7 Exercises 225
6 Vibrational Spectroscopy of Polyatomic Molecules 231
6.1 Introduction 231
6.2 Normal Modes of Vibration of Carbon Dioxide 231
6.2.1 Properties of normal modes 237
6.2.2 Selection rules for carbon dioxide 238
6.2.3 Vibration-rotation spectra of symmetric top molecules 241
6.2.4 Symmetries of normal modes 242
6.2.5 Selection rules 250
6.2.6 Higher vibrational wave functions 256
6.2.7 Combination bands 257
6.3 Summary 260
6.4 Exercises 260
7 The Raman Effect 263
7.1 Introduction 263
7.2 Classical Treatment of the Raman Effect 264
7.2.1 Polarizability 264
viii Contents
7.2.2 Molecular rotations 265
7.2.3 Molecular vibrations 266
7.3 Quantum Theory 267
7.3.1 Polarizability ellipsoid 267
7.3.2 Selection rules 270
7.4 Rule of Mutual Exclusion 277
7.5 Polarization of Raman Lines 279
7.6 Fermi Resonance 282
7.7 Influence of Nuclear Spin 284
7.8 Structure Determination Using Combined Infrared and
Raman Data 289
7.8.1 Examples of spectral assignments 290
7.9 Group Frequencies 297
7.10 Comparison of IR and Raman spectroscopies 299
7.11 Advanced Raman Techniques 299
7.12 Summary 300
7.13 Exercises 300
8 Electronic Spectroscopy of Diatomic Molecules 305
8.1 Introduction 305
8.2 The Bom-Oppenheimer Approximation 305
8.3 Vibrational Coarse Structure 307
8.4 Franck-Condon Principle 308
8.5 Dissociation Energy 311
8.5.1 The Franck-Condon factor: Quantum mechanical treatment 314
8.6 Electronic Structure of Diatomic Molecules 316
8.6.1 Homonuclear diatomic molecules 322
8.6.2 Heteronuclear diatomic molecules 324
8.7 Electronic Angular Momentum in Diatomic Molecules 328
8.7.1 Completely filled shells 328
8.7.2 Single unpaired electron 328
8.7.3 Two unpaired electrons 329
8.8 Selection Rules 331
8.9 Rotational Fine Structure of Electronic-Vibrational Transitions 334
8.9.1 The Fortrat diagram 336
8.10 Photoelectron Spectroscopy (PES) 337
8.11 Summary 342
8.12 Exercises 342
9 Electronic Spectroscopy of Polyatomic Molecules 346
9.1 Introduction 346
9.2 Intensities of Electronic Transitions 346
9.2.1 Calculation of oscillator strength 347
Contents ix
9.3 Types of Electronic Transitions 349
9.3.1 Effect of conjugation 352
9.3.2 Effect of solvent 354
9.4 Theories of Transitions 355
9.4.1 Hiickel molecular orbital (HMO) theory 356
9.5 Free Electron Model of Linear Polyenes 365
9.5.1 Calculation of the wave functions 366
9.5.2 Energy of the longest wavelength transition in polyenes 366
9.5.3 Selection rules for particle-in-a-box wave functions 370
9.6 Change of Molecular Shape on Absorption 372
9.6.1 AH2 molecules 372
9.6.2 The electronic structure of formaldehyde 377
9.7 Vibronic Coupling 380
9.8 Re-emission of Energy by an Excited Molecule 381
9.9 Kinetics of Photochemistry 385
9.10 Summary 389
9.11 Exercises 389
Appendix 1 397
Appendix 2 399
Bibliography 403
Index 405
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| indexdate | 2024-07-10T01:16:07Z |
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| isbn | 9781107063884 |
| language | English |
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| spelling | Kakkar, Rita Verfasser (DE-588)1072042886 aut Atomic and molecular spectroscopy basic concepts and applications Rita Kakkar Delhi Cambridge Univ. Press 2015 XX, 415 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Includes bibliographical references and index "Elucidates various spectroscopic techniques including atomic spectroscopy, pure rotational spectroscopy, vibrational spectroscopy of diatomic and polyatomic molecules, Raman spectroscopy and electronic spectroscopy"-- Molekülspektroskopie (DE-588)4128850-6 gnd rswk-swf Atomspektroskopie (DE-588)4143333-6 gnd rswk-swf Atomspektroskopie (DE-588)4143333-6 s DE-604 Molekülspektroskopie (DE-588)4128850-6 s Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=027677143&sequence=000003&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Klappentext Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=027677143&sequence=000004&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
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| title | Atomic and molecular spectroscopy basic concepts and applications |
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| title_short | Atomic and molecular spectroscopy |
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