Spectra Of Atoms And Molecules

by Bernath, Peter F.

• ISBN13: 9780195177596
• ISBN10: 0195177592
• Edition: 2nd
• Format: Hardcover
• Copyright: 2005-04-21
• Publisher: Oxford University Press

Summary

Spectra of Atoms and Molecules, 2nd Edition is designed to introduce advanced undergraduates and new graduate students to the vast field of spectroscopy. Of interest to chemists, physicists, astronomers, atmospheric scientists, and engineers, it emphasizes the fundamental principles ofspectroscopy with its primary goal being to teach students how to interpret spectra. The book includes a clear presentation of group theory needed for understanding the material and a large number of excellent problems are found at the end of each chapter. In keeping with the visual aspects of thecourse, the author provides a large number of diagrams and spectra specifically recorded for this book. Topics such as molecular symmetry, matrix representation of groups, quantum mechanics, and group theory are discussed. Analyses are made of atomic, rotational, vibrational, and electronic spectra. Spectra of Atoms and Molecules, 2nd Edition has been updated to include the 1998 revision of physical constants, and conforms more closely to the recommended practice for the use of symbols and units. This new edition has also added material pertaining to line intensities, which can be confusingdue to the dozens of different units used to report line and band strengths. Another major change is in author Peter Bernath's discussion of the Raman effect and light scattering, where the standard theoretical treatment is now included. Aimed at new students of spectroscopy regardless of theirbackground, Spectra of Atoms and Molecules will help demystify spectroscopy by showing the necessary steps in a derivation.

Author Biography

Peter F. Bernath is Professor of Chemistry, at the University of Waterloo in Ontario, Canada.

Table of Contents

Introduction	1	(42)
Waves, Particles, and Units	1	(2)
The Electromagnetic Spectrum	3	(2)
Interaction of Radiation with Matter	5	(38)
Blackbody Radiation	5	(2)
Einstein A and B Coefficients	7	(3)
Absorption and Emission of Radiation	10	(8)
Beer's Law	18	(2)
Lineshape Functions	20	(1)
Natural Lifetime Broadening	21	(6)
Pressure Broadening	27	(1)
Doppler Broadening	28	(2)
Transit-Time Broadening	30	(2)
Power Broadening	32	(11)
Molecular Symmetry	43	(18)
Symmetry Operations	43	(8)
Operator Algebra	44	(4)
Symmetry Operator Algebra	48	(3)
Groups	51	(3)
Point Groups	51	(2)
Classes	53	(1)
Subgroups	54	(1)
Notation for Point Groups	54	(7)
Matrix Representation of Groups	61	(35)
Vectors and Matrices	61	(8)
Matrix Eigenvalue Problem	67	(2)
Similarity Transformations	69	(1)
Symmetry Operations and Position Vectors	69	(4)
Reflection	70	(1)
Rotation	70	(2)
Inversion	72	(1)
Rotation-Reflection	72	(1)
Identity	73	(1)
Symmetry Operators and Basis Vectors	73	(3)
Symmetry Operators and Basis Functions	76	(5)
Function Spaces	77	(1)
Gram-Schmidt Procedure	78	(1)
Transformation Operators	79	(2)
Equivalent, Reducible, and Irreducible Representations	81	(2)
Equivalent Representations	81	(1)
Unitary Representations	82	(1)
Reducible and Irreducible Representations	82	(1)
Great Orthogonality Theorem	83	(5)
Characters	86	(2)
Character Tables	88	(8)
Mulliken Notation	89	(7)
Quantum Mechanics and Group Theory	96	(20)
Matrix Representation of the Schrodinger Equation	96	(6)
Born-Oppenheimer Approximation	102	(3)
Symmetry of the Hamiltonian Operator	105	(2)
Projection Operators	107	(3)
Direct Product Representations	110	(1)
Integrals and Selection Rules	111	(5)
Atomic Spectroscopy	116	(56)
Background	116	(2)
Angular Momentum	118	(5)
The Hydrogen Atom and One-Electron Spectra	123	(10)
Vector Model	126	(2)
Spin-Orbit Coupling	128	(5)
Many-Electron Atoms	133	(9)
Selection Rules	142	(4)
Atomic Spectra	146	(4)
Hyperfine Structure	147	(2)
Hydrogen Atom	149	(1)
Intensity of Atomic Lines	150	(7)
Zeeman Effect	157	(5)
Paschen-Back Effect	162	(1)
Stark Effect	162	(10)
Rotational Spectroscopy	172	(49)
Rotation of Rigid Bodies	172	(8)
Diatomic and Linear Molecules	180	(13)
Selection Rules	182	(4)
Centrifugal Distortion	186	(2)
Vibrational Angular Momentum	188	(5)
Line Intensities for Diatomic and Linear Molecules	193	(4)
Symmetric Tops	197	(8)
Molecule and Space-Fixed Angular Momenta	198	(5)
Rotational Spectra	203	(1)
Centrifugal Distortion	204	(1)
Line Intensity	205	(1)
Asymmetric Tops	205	(6)
Selection Rules	208	(3)
Line Intensity	211	(1)
Structure Determination	211	(10)
Vibrational Spectroscopy	221	(90)
Diatomic Molecules	221	(19)
Wavefunctions for Harmonic and Anharmonic Oscillators	229	(1)
Vibrational Selection Rules for Diatomics	230	(4)
Dissociation Energies from Spectroscopic Data	234	(2)
Vibration-Rotation Transitions of Diatomics	236	(2)
Combination Differences	238	(2)
Vibrational Motion of Polyatomic Molecules	240	(35)
Classical Mechanical Description	240	(5)
Quantum Mechanical Description	245	(2)
Internal Coordinates	247	(1)
Symmetry Coordinates	247	(6)
Symmetry of Normal Modes	253	(8)
Selection Rules for Vibrational Transitions	261	(2)
Vibration-Rotation Transitions of Linear Molecules	263	(6)
Nuclear Spin Statistics	269	(4)
Excited Vibrational States of Linear Molecules	273	(2)
Vibrational Spectra of Symmetric Tops	275	(7)
Coriolis Interactions in Molecules	276	(6)
Infrared Transitions of Spherical Tops	282	(4)
Vibrational Spectra of Asymmetric Tops	286	(3)
Vibration-Rotation Line Intensities	289	(6)
Line Intensity Calculations	292	(3)
Fermi and Coriolis Perturbations	295	(2)
Inversion Doubling and Fluxional Behavior	297	(14)
Light Scattering and the Raman Effect	311	(30)
Background	311	(14)
Classical Model	311	(6)
Quantum Model	317	(7)
Polarization	324	(1)
Rotational Raman Effect	325	(3)
Diatomic Molecules	327	(1)
Vibration-Rotation Raman Spectroscopy	328	(1)
Diatomic Molecules	328	(1)
Rayleigh and Raman Intensities	329	(7)
Classical Theory	329	(5)
Vibrational Intensity Calculations	334	(2)
Conclusions	336	(5)
Electronic Spectroscopy of Diatomics	341	(48)
Orbitals and States	341	(6)
Vibrational Structure	347	(5)
Rotational Structure of Diatomic Molecules	352	(15)
Singlet-Singlet Transitions	352	(6)
Nonsinglet Transitions	358	(9)
The Symmetry of Diatomic Energy Levels: Parity	367	(8)
Total (+/-) Parity	368	(3)
Rotationless (e/f) Parity	371	(1)
Gerade/Ungerade (g/u) Parity	372	(1)
Symmetric/Antisymmetric (s/a) Parity	373	(2)
Rotational Line Intensities	375	(6)
Dissociation, Photodissociation, and Predissociation	381	(8)
Units, Conversions, and Physical Constants	389	(2)
Character Tables	391	(12)
Direct Product Tables	403	(4)
Introductory Textbooks	407	(20)
Figure Acknowledgments	427	(4)
Index	431