Fundamentals of Molecular Symmetry
By: P.R. Bunker, P. Jensen
Paperback | 1 November 2004 | Edition Number 1
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378 Pages
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Industry Reviews
Winner of a 2005 CHOICE Outstanding Academic Book Award!
"For more than 25 years, Molecular Symmetry and Spectroscopy ... and the subsequent second edition ... have been this reviewer's most trusted authority and treasured references on the role of symmetry in molecular spectroscopy ... . The book starts with a beautifully concise yet complete review of spectroscopy and quantum mechanics ... . A fine balance is struck in the level of detail provided. ... Summing up: highly recommended."
- CHOICE Reviews online
"This book provides a welcome slant on molecular symmetry, for those who worry that rigid ball and stick point group arguments to ignore the geometrical distortions accompanying molecular vibrations. In summary, this book is welcome, first as an illuminating graduate text and also as an addition to the shelves of anyone who is responsible for teaching molecular symmetry at whatever level."
- Mark Child, Chemistry World, March 2005
"This book is of primary importance in training new scientists in the field of molecular spectroscopy and quantum chemistry, i.e., in branches of modern science that attract increasing interest nowadays. It is particularly important that reading this book helps readers to form their correct general scientific philosophy."
- Dr. Yurii N. Panchenko, Moscow State University, Russia
"As a resource for a starting out research students and other workers in electronic structure and bonding and high resolution spectroscopy it would serve as a very useful introduction to the more advanced aspects of symmetry. It would be a welcome presence on the research lab bookshelves, and would hopefully show signs of much use."
- Nigel A. Young, Department of Chemistry, University of Hull, in Physical Sciences Educational Review, Vol. 6, No. 1
"Fundamentals of Molecular Symmetry is an excellent book. ...The title thus belies the true content of the book; it covers so much more than most other books on molecular symmetry. As such it should be an essential text for any graduate student or established researcher working in the area of high-resolution spectroscopy. ...Fundamentals of Molecular Symmetry is exceptionally well written and up to the very high standards set by the authors in their previous texts. It is clearly written and the figures and diagrams are beautifully produced. There are numerous figures of orbital shapes, energy-level diagrams and molecular spectra. Readers will also particularly appreciate the way each concept is illustrated by examples of application to real molecular systems. Fundamentals of Molecular Symmetry has my unqualified recommendation."
-Dr. D. Smith, Contemporary Physics
Preface | p. xi |
Spectroscopy and the quantum states of molecules | p. 1 |
Molecular spectroscopy | p. 3 |
Molecular spectra | p. 3 |
The energies of molecules in the gas phase | p. 6 |
The positions of spectral lines | p. 9 |
The intensities of spectral lines | p. 11 |
The shapes of spectral lines | p. 12 |
Raman spectra | p. 14 |
Problems | p. 15 |
Quantum mechanics | p. 17 |
The Schrodinger equation | p. 17 |
The postulates of quantum mechanics | p. 18 |
Operators and eigenfunctions | p. 19 |
Diagonalizing the Hamiltonian matrix | p. 21 |
The molecular Schrodinger equation | p. 26 |
The separation of translational energy | p. 26 |
The translational Schrodinger equation | p. 29 |
The rovibronic Schrodinger equation | p. 32 |
The angular momentum operator | p. 34 |
The dipole moment operator and line strengths | p. 35 |
Matrices and matrix algebra | p. 37 |
Problems | p. 40 |
Electronic states | p. 42 |
The Born-Oppenheimer approximation | p. 42 |
Spin and the Pauli exclusion principle | p. 46 |
Electronic wavefunctions and energies | p. 48 |
The Slater determinant | p. 49 |
The Hartree-Fock approximation and molecular orbitals | p. 50 |
MOs as linear combinations of atomic orbitals | p. 52 |
Configuration interaction | p. 52 |
Molecular orbital theory | p. 53 |
Bonding and antibonding orbitals | p. 54 |
Hybridization | p. 57 |
The Huckel approximation and benzene | p. 61 |
Polyene chain molecules | p. 62 |
Problems | p. 65 |
Vibrational states | p. 68 |
Space-fixed and molecule-fixed axes | p. 68 |
The vibrational Hamiltonian | p. 70 |
Vibrational wavefunctions and energies | p. 72 |
Anharmonicity | p. 78 |
Tunnelling | p. 81 |
Problems | p. 87 |
Rotational states | p. 89 |
The Euler angles | p. 89 |
The principal moments of inertia | p. 90 |
The rigid-rotor Hamiltonian | p. 92 |
Symmetric top molecules | p. 92 |
Linear molecules | p. 94 |
Spherical top molecules | p. 95 |
Asymmetric top molecules | p. 95 |
Rovibronic wavefunctions | p. 96 |
The Hamiltonian and wavefunctions in detail | p. 97 |
The derivation of the rigid-rotor Hamiltonian | p. 97 |
The Euler angles and angular momentum | p. 99 |
The symmetric top wavefunctions | p. 101 |
The asymmetric top wavefunctions and energies | p. 101 |
Problems | p. 107 |
Symmetry and symmetry groups | p. 111 |
Geometrical symmetry | p. 113 |
Geometrical symmetry operations | p. 113 |
Geometrical symmetry groups: Point groups | p. 117 |
The point group symmetry of molecules | p. 122 |
Problems | p. 125 |
The symmetry of the Hamiltonian | p. 126 |
Hamiltonian symmetry operations | p. 126 |
Nuclear permutations and the inversion E* | p. 127 |
Symmetry labels | p. 132 |
Symmetry groups | p. 133 |
The vanishing integral rule | p. 136 |
Proof of the vanishing integral rule for the water molecule | p. 138 |
Selection rules | p. 139 |
The rovibronic symmetry label J | p. 140 |
Diagonalizing the Hamiltonian matrix using symmetry | p. 141 |
The Stark effect | p. 142 |
The symmetry of H[subscript 3] | p. 143 |
Group theory | p. 149 |
Problems | p. 156 |
The symmetry groups of rigid molecules | p. 158 |
The CNPI group | p. 158 |
The molecular symmetry (MS) group | p. 162 |
The MS group and the point group | p. 164 |
The H[subscript 2]O molecule | p. 164 |
The H[subscript 3] molecule | p. 168 |
General rules for rigid molecule symmetry groups | p. 171 |
Linear rigid molecules | p. 172 |
The ethylene molecule C[subscript 2]H[subscript 4] | p. 173 |
Problems | p. 175 |
Applications of symmetry | p. 177 |
Nuclear spin, statistical weights and hyperfine structure | p. 179 |
The fifth postulate of quantum mechanics | p. 179 |
Statistical weights | p. 180 |
Missing levels | p. 184 |
CO[subscript 2] | p. 184 |
H[superscript + subscript 3] | p. 185 |
Statistical weights for CH[subscript 3]F | p. 186 |
Nuclear spin hyperfine structure | p. 187 |
Problems | p. 191 |
The symmetry of electronic wavefunctions | p. 193 |
The water molecule | p. 193 |
The benzene molecule | p. 197 |
The butadiene molecule | p. 205 |
Conservation of orbital symmetry | p. 207 |
The non-crossing rule | p. 217 |
The C[subscript 6] and [sigma subscript v] operations for benzene | p. 218 |
Problems | p. 220 |
The symmetry of rotation-vibration wavefunctions | p. 222 |
The transformation properties of the Euler angles | p. 222 |
The symmetry of rotational wavefunctions | p. 224 |
H[superscript + subscript 3] | p. 226 |
H[subscript 2]O | p. 229 |
The symmetry of normal coordinates | p. 230 |
H[subscript 2]O | p. 232 |
Benzene | p. 233 |
The symmetry of vibrational wavefunctions | p. 236 |
H[subscript 2]O | p. 236 |
H[superscript + subscript 3] | p. 236 |
Rotation-vibration coupling | p. 238 |
Problems | p. 244 |
Symmetry selection rules for optical transitions | p. 245 |
Forbidden and allowed transitions | p. 245 |
Zero-order transition moment integrals | p. 247 |
Transitions within an electronic state | p. 249 |
Vibrational transition moments and Honl-London factors | p. 249 |
The rotational spectrum of the CO molecule | p. 255 |
Parallel and perpendicular bands of CH[subscript 3]F | p. 255 |
Rotation-vibration interaction | p. 261 |
Transitions between electronic states | p. 264 |
Raman transitions | p. 266 |
Problems | p. 272 |
The symmetry groups of non-rigid molecules | p. 274 |
The MS group of a non-rigid molecule | p. 274 |
The ammonia molecule | p. 275 |
Torsionally tunnelling ethylene | p. 278 |
Intensity alternations for HSSH and DSSD | p. 280 |
The water dimer and the water trimer | p. 282 |
Water dimer | p. 282 |
Water trimer | p. 287 |
Ethylene and its Raman spectrum | p. 288 |
Problems | p. 290 |
Other symmetries and symmetry violation | p. 291 |
Other symmetries | p. 293 |
The fourth postulate of quantum mechanics | p. 293 |
Conservation laws | p. 294 |
Electron permutation symmetry | p. 295 |
Translational symmetry | p. 296 |
Rotational symmetry | p. 301 |
Charge conjugation | p. 304 |
Parity | p. 305 |
Time reversal | p. 308 |
Symmetry violation | p. 310 |
The electroweak Hamiltonian | p. 310 |
Parity (P) violation | p. 311 |
CP violation | p. 313 |
T violation | p. 315 |
Testing for CPT violation | p. 316 |
Testing for permutation symmetry violation | p. 316 |
Answers to selected problems | p. 320 |
Character tables | p. 331 |
Books for further reading | p. 352 |
Index | p. 354 |
Table of Contents provided by Rittenhouse. All Rights Reserved. |
ISBN: 9780750309417
ISBN-10: 0750309415
Series: Series in Chemical Physics
Published: 1st November 2004
Format: Paperback
Language: English
Number of Pages: 378
Audience: College, Tertiary and University
Publisher: Taylor & Francis Ltd
Country of Publication: GB
Edition Number: 1
Dimensions (cm): 23.39 x 15.6 x 1.98
Weight (kg): 0.64
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