Electronic and Photoelectron Spectroscopy: Fundamentals and Case Studies

by Andrew M. Ellis , Miklos Feher , Timothy G. Wright

• ISBN13: 9780521520638
• ISBN10: 0521520630
• Edition: Revised
• Format: Paperback
• Copyright: 2011-04-14
• Publisher: Cambridge University Press

Summary

Electronic and photoelectron spectroscopy provides extraordinarily detailed information on the properties of molecules. This book presents the basic principles and experimental techniques employed in electronic and photoelectron spectroscopy. A major feature is the extensive use of case studies to illustrate how spectra are assigned and how information can be extracted. The text is intended for advanced undergraduate and graduate students studying courses in spectroscopy.

Table of Contents

Preface	p. xi
List of journal abbreviations	p. xiii
Foundations of electronic and photoelectron spectroscopy	p. 1
Introduction	p. 3
The basics	p. 3
Information obtained from electronic and photoelectron spectra	p. 5
Electronic structure	p. 7
Orbitals: quantum mechanical background	p. 7
References	p. 11
Angular momentum in spectroscopy	p. 12
Classification of electronic states	p. 15
Atoms	p. 15
Molecules	p. 17
References	p. 23
Molecular vibrations	p. 24
Diatomic molecules	p. 24
Polyatomic molecules	p. 31
References	p. 39
Molecular rotations	p. 40
Diatomic molecules	p. 40
Polyatomic molecules	p. 43
Transition probabilities	p. 51
Transition moments	p. 51
Factorization of the transition moment	p. 56
References	p. 64
Experimental techniques	p. 65
The sample	p. 67
Thermal sources	p. 67
Supersonic jets	p. 68
Matrix isolation	p. 72
References	p. 74
Broadening of spectroscopic lines	p. 75
Natural broadening	p. 75
Doppler broadening	p. 76
Pressure broadening	p. 77
Lasers	p. 78
Properties	p. 78
Basic principles	p. 79
Ion lasers	p. 81
Nd: YAG laser	p. 81
Excimer laser	p. 82
Dye lasers	p. 83
Titanium:sapphire laser	p. 85
Optical parametric oscillators	p. 86
References	p. 86
Optical spectroscopy	p. 87
Conventional absorption/emission spectroscopy	p. 87
Laser-induced fluorescence (LIF) spectroscopy	p. 89
Cavity ringdown (CRD) laser absorption spectroscopy	p. 92
Resonance-enhanced multiphoton ionization (REMPI) spectroscopy	p. 94
Double-resonance spectroscopy	p. 96
Fourier transform (FT) spectroscopy	p. 97
References	p. 101
Photoelectron spectroscopy	p. 102
Conventional ultraviolet photoelectron spectroscopy	p. 102
Synchrotron radiation in photoelectron spectroscopy	p. 105
Negative ion photoelectron spectroscopy	p. 105
Penning ionization electron spectroscopy	p. 107
Zero electron kinetic energy (ZEKE) spectroscopy	p. 107
ZEKE-PFI spectroscopy	p. 110
Reference	p. 110
Further reading	p. 110
Case Studies	p. 111
Ultraviolet photoelectron spectrum of CO	p. 113
Electronic structures of CO and CO[superscript +]	p. 113
First photoelectron band system	p. 115
Second photoelectron band system	p. 115
Third photoelectron band system	p. 116
Adiabatic and vertical ionization energies	p. 116
Intensities of photoelectron band systems	p. 117
Determining bond lengths from Franck-Condon factor calculations	p. 118
References	p. 119
Photoelectron spectra of CO[subscript 2], OCS, and CS[subscript 2] in a molecular beam	p. 120
First photoelectron band system	p. 123
Second photoelectron band system	p. 125
Thrid and fourth photoelectron band systems	p. 126
Electronic structures: constructing an MO diagram from photoelectron spectra	p. 126
References	p. 128
Photoelectron spectrum of NO[subscript 2 superscript -]	p. 129
The experiment	p. 129
Vibrational structure	p. 130
Vibrational constants	p. 132
Structure determination	p. 132
Electron affinity and thermodynamic parameters	p. 134
Electronic structure	p. 134
References	p. 137
Laser-induced fluorescence spectroscopy of C[subscript 3]: rotational structure in the 300 nm system	p. 138
Electronic structure and selection rules	p. 138
Assignment and analysis of the rotational structure	p. 141
Band head formation	p. 143
References	p. 143
Photoionization spectrum of diphenylamine: an unusual illustration of the Franck-Condon principle	p. 144
References	p. 149
Vibrational structure in the electronic spectrum of 1,4-benzodioxan: assignment of low frequency modes	p. 150
Ab initio calculations	p. 152
Assigning the spectra	p. 152
References	p. 156
Vibrationally resolved ultraviolet spectroscopy of propynal	p. 157
Electronic states	p. 159
Assigning the vibrational structure	p. 159
LIF spectroscopy of jet-cooled propynal	p. 161
References	p. 164
Rotationally resolved laser excitation spectrum of propynal	p. 165
Assigning the rotational structure	p. 165
Perpendicular versus parallel character	p. 167
Rotational constants	p. 168
Effects of asymmetry	p. 168
References	p. 170
ZEKE spectroscopy of Al(H[subscript 2]O) and Al(D[subscript 2]O)	p. 171
Experimental details	p. 172
Assignment of the vibrationally resolved spectrum	p. 172
Dissociation energies	p. 175
Rotational structure	p. 177
Bonding in Al(H[subscript 2]O)	p. 178
References	p. 179
Rotationally resolved electronic spectroscopy of the NO free radical	p. 180
References	p. 186
Vibrationally resolved spectroscopy of Mg[superscript +]-rare gas complexes	p. 187
Experimental details	p. 188
Preliminaries: electronic states	p. 189
Photodissociation spectra	p. 190
Spin-orbit coupling	p. 190
Vibrational assignment	p. 193
Vibrational frequencies	p. 194
Dissociation energies	p. 195
B-X system	p. 196
References	p. 196
Rotationally resolved spectroscopy of Mg[superscript +]-rare gas complexes	p. 197
X[superscript 2 Sigma superscript +] state	p. 197
A[superscript 2 Pi] state	p. 199
Transition energies and selection rules	p. 200
Photodissociation spectra of Mg[superscript +]-Ne and Mg[superscript +]-Ar	p. 201
References	p. 204
Vibronic coupling in benzene	p. 205
The Herzberg-Teller effect	p. 208
References	p. 209
REMPI spectroscopy of chlorobenzene	p. 210
Experimental details and spectrum	p. 211
Assignment	p. 212
References	p. 215
Spectroscopy of the chlorobenzene cation	p. 216
The X[superscript 2]B[subscript 1] state	p. 216
The B state	p. 221
References	p. 222
Cavity ringdown spectroscopy of the [characters not reproducible] transition in O[subscript 2]	p. 223
Experimental	p. 223
Electronic states of O[subscript 2]	p. 225
Rotational energy levels	p. 226
Nuclear spin statistics	p. 227
Spectrum assignment	p. 228
Why is this strongly forbidden transition observed?	p. 229
References	p. 229
Units in spectroscopy	p. 230
Some fundamental constants and useful unit conversions	p. 231
Electronic structure calculations	p. 232
Preliminaries	p. 232
Hartree-Fock method	p. 234
Semiempirical methods	p. 237
Beyond the Hartree-Fock method: allowing for electron correlation	p. 238
Density functional theory (DFT)	p. 239
Software packages	p. 240
Calculation of molecular properties	p. 240
References	p. 242
Further reading	p. 242
Coupling of angular momenta: electronic states	p. 243
Coupling in the general case: the basics	p. 244
Coupling of angular momenta in atoms	p. 244
Coupling of electronic angular momenta in linear molecules	p. 246
Non-linear molecules	p. 248
Further reading	p. 248
The principles of point group symmetry and group theory	p. 249
Symmetry elements and operations	p. 249
Point groups	p. 251
Classes and multiplication tables	p. 252
The matrix representation of symmetry operations	p. 254
Character tables	p. 256
Reducible representations, direct products, and direct product tables	p. 257
Cyclic and linear groups	p. 259
Symmetrized and antisymmetrized products	p. 261
Further reading	p. 261
Selected character tables	p. 262
More on electronic configurations and electronic states: degenerate orbitals and the Pauli principle	p. 266
Atoms	p. 266
Molecules	p. 268
Nuclear spin statistics	p. 269
Fermionic nuclei	p. 270
Bosonic nuclei	p. 270
Coupling of angular momenta: Hund's coupling cases	p. 272
Hund's case (a)	p. 272
Hund's case (b)	p. 274
Other Hund's coupling cases	p. 276
Further reading	p. 276
Computational simulation and analysis of rotational structure	p. 277
Calculating rotational energy levels	p. 277
Calculating transition intensities	p. 279
Determining spectroscopic constants	p. 279
References	p. 280
Further reading	p. 281
Index	p. 282
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