Electronic and photoelectron spectroscopy : fundamentals and case studies

Title:

Personal Author:

Ellis, Andrew M (Andrew Michael), 1963-

Publication Information:

Cambridge : Cambridge University Press, 2005

ISBN:

9780521817370

Subject Term:

Photoelectron spectroscopy -- Study and teaching

Electron spectroscopy -- Study and teaching

Added Author:

Feher, Miklos, 1960-

Wright, Timothy G. (Timothy Grahame), 1965-

Available:*

Library	Item Barcode	Call Number	Material Type	Item Category 1	Status
Searching... PSZ JB	30000004729178	QC454.P48 E44 2005	Open Access Book	Book	Searching... Unknown

Electronic and photoelectron spectroscopy can provide extraordinarily detailed information on the properties of molecules and are in widespread use in the physical and chemical sciences. Applications extend beyond spectroscopy into important areas such as chemical dynamics, kinetics and atmospheric chemistry. This book aims to provide the reader with a firm grounding of the basic principles and experimental techniques employed. The extensive use of case studies effectively illustrates how spectra are assigned and how information can be extracted, communicating the matter in a compelling and instructive manner. Topics covered include laser-induced fluorescence, resonance-enhanced multiphoton ionization, cavity ringdown and ZEKE spectroscopy. The volume is for advanced undergraduate and graduate students taking courses in spectroscopy and will also be useful to anyone encountering electronic and/or photoelectron spectroscopy during their research.

Reviews 1

Choice Review

This book is designed to be a guide and reference work to electronic and photoelectron spectroscopy. Ellis (Univ. of Leicester, UK), Feher (industry), and Wright (Univ. of Nottingham, UK) aim their book at advanced undergraduate students in chemistry as well as graduate students and researchers in analytical chemistry and allied areas. The book takes a unique approach--instead of just discussing the fundamentals of electron and photoelectron spectroscopy with some general applications, it discusses the latest research in these areas. This can be difficult, as research books do not ordinarily spend much time discussing fundamental principles and tend to be heavy with jargon. Here, the authors take state-of-the-art research reports and dissect and explain them so the reader can appreciate the elegance and value of scientific research. They devote about the first third of the book to a concise, useful discussion of the fundamentals of these two techniques. Topics include the theory of electronic and photoelectronic spectroscopy and major experimental techniques, followed by case studies. For a scientist with a solid math and chemistry background, this is an excellent book on spectroscopy. ^BSumming Up: Highly recommended. Upper-division undergraduates through professionals. J. A. Siegel Indiana University-Purdue University Indianapolis

Preface	p. xi
List of journal abbreviations	p. xiii
Part I Foundations of electronic and photoelectron spectroscopy	p. 1
1 Introduction	p. 3
1.1 The basics	p. 3
1.2 Information obtained from electronic and photoelectron spectra	p. 5
2 Electronic structure	p. 7
2.1 Orbitals: quantum mechanical background	p. 7
References	p. 11
3 Angular momentum in spectroscopy	p. 12
4 Classification of electronic states	p. 15
4.1 Atoms	p. 15
4.2 Molecules	p. 17
References	p. 23
5 Molecular vibrations	p. 24
5.1 Diatomic molecules	p. 24
5.2 Polyatomic molecules	p. 31
References	p. 39
6 Molecular rotations	p. 40
6.1 Diatomic molecules	p. 40
6.2 Polyatomic molecules	p. 43
7 Transition probabilities	p. 51
7.1 Transition moments	p. 51
7.2 Factorization of the transition moment	p. 56
References	p. 64
Part II Experimental techniques	p. 65
8 The sample	p. 67
8.1 Thermal sources	p. 67
8.2 Supersonic jets	p. 68
8.3 Matrix isolation	p. 72
References	p. 74
9 Broadening of spectroscopic lines	p. 75
9.1 Natural broadening	p. 75
9.2 Doppler broadening	p. 76
9.3 Pressure broadening	p. 77
10 Lasers	p. 78
10.1 Properties	p. 78
10.2 Basic principles	p. 79
10.3 Ion lasers	p. 81
10.4 Nd: YAG laser	p. 81
10.5 Excimer laser	p. 82
10.6 Dye lasers	p. 83
10.7 Titanium:sapphire laser	p. 85
10.8 Optical parametric oscillators	p. 86
References	p. 86
11 Optical spectroscopy	p. 87
11.1 Conventional absorption/emission spectroscopy	p. 87
11.2 Laser-induced fluorescence (LIF) spectroscopy	p. 89
11.3 Cavity ringdown (CRD) laser absorption spectroscopy	p. 92
11.4 Resonance-enhanced multiphoton ionization (REMPI) spectroscopy	p. 94
11.5 Double-resonance spectroscopy	p. 96
11.6 Fourier transform (FT) spectroscopy	p. 97
References	p. 101
12 Photoelectron spectroscopy	p. 102
12.1 Conventional ultraviolet photoelectron spectroscopy	p. 102
12.2 Synchrotron radiation in photoelectron spectroscopy	p. 105
12.3 Negative ion photoelectron spectroscopy	p. 105
12.4 Penning ionization electron spectroscopy	p. 107
12.5 Zero electron kinetic energy (ZEKE) spectroscopy	p. 107
12.6 ZEKE-PFI spectroscopy	p. 110
Reference	p. 110
Further reading	p. 110
Part III Case Studies	p. 111
13 Ultraviolet photoelectron spectrum of CO	p. 113
13.1 Electronic structures of CO and CO[superscript +]	p. 113
13.2 First photoelectron band system	p. 115
13.3 Second photoelectron band system	p. 115
13.4 Third photoelectron band system	p. 116
13.5 Adiabatic and vertical ionization energies	p. 116
13.6 Intensities of photoelectron band systems	p. 117
13.7 Determining bond lengths from Franck-Condon factor calculations	p. 118
References	p. 119
14 Photoelectron spectra of CO[subscript 2], OCS, and CS[subscript 2] in a molecular beam	p. 120
14.1 First photoelectron band system	p. 123
14.2 Second photoelectron band system	p. 125
14.3 Thrid and fourth photoelectron band systems	p. 126
14.4 Electronic structures: constructing an MO diagram from photoelectron spectra	p. 126
References	p. 128
15 Photoelectron spectrum of NO[subscript 2 superscript -]	p. 129
15.1 The experiment	p. 129
15.2 Vibrational structure	p. 130
15.3 Vibrational constants	p. 132
15.4 Structure determination	p. 132
15.5 Electron affinity and thermodynamic parameters	p. 134
15.6 Electronic structure	p. 134
References	p. 137
16 Laser-induced fluorescence spectroscopy of C[subscript 3]: rotational structure in the 300 nm system	p. 138
16.1 Electronic structure and selection rules	p. 138
16.2 Assignment and analysis of the rotational structure	p. 141
16.3 Band head formation	p. 143
References	p. 143
17 Photoionization spectrum of diphenylamine: an unusual illustration of the Franck-Condon principle	p. 144
References	p. 149
18 Vibrational structure in the electronic spectrum of 1,4-benzodioxan: assignment of low frequency modes	p. 150
18.1 Ab initio calculations	p. 152
18.2 Assigning the spectra	p. 152
References	p. 156
19 Vibrationally resolved ultraviolet spectroscopy of propynal	p. 157
19.1 Electronic states	p. 159
19.2 Assigning the vibrational structure	p. 159
19.3 LIF spectroscopy of jet-cooled propynal	p. 161
References	p. 164
20 Rotationally resolved laser excitation spectrum of propynal	p. 165
20.1 Assigning the rotational structure	p. 165
20.2 Perpendicular versus parallel character	p. 167
20.3 Rotational constants	p. 168
20.4 Effects of asymmetry	p. 168
References	p. 170
21 ZEKE spectroscopy of Al(H[subscript 2]O) and Al(D[subscript 2]O)	p. 171
21.1 Experimental details	p. 172
21.2 Assignment of the vibrationally resolved spectrum	p. 172
21.3 Dissociation energies	p. 175
21.4 Rotational structure	p. 177
21.5 Bonding in Al(H[subscript 2]O)	p. 178
References	p. 179
22 Rotationally resolved electronic spectroscopy of the NO free radical	p. 180
References	p. 186
23 Vibrationally resolved spectroscopy of Mg[superscript +]-rare gas complexes	p. 187
23.1 Experimental details	p. 188
23.2 Preliminaries: electronic states	p. 189
23.3 Photodissociation spectra	p. 190
23.4 Spin-orbit coupling	p. 190
23.5 Vibrational assignment	p. 193
23.6 Vibrational frequencies	p. 194
23.7 Dissociation energies	p. 195
23.8 B-X system	p. 196
References	p. 196
24 Rotationally resolved spectroscopy of Mg[superscript +]-rare gas complexes	p. 197
24.1 X[superscript 2 Sigma superscript +] state	p. 197
24.2 A[superscript 2 Pi] state	p. 199
24.3 Transition energies and selection rules	p. 200
24.4 Photodissociation spectra of Mg[superscript +]-Ne and Mg[superscript +]-Ar	p. 201
References	p. 204
25 Vibronic coupling in benzene	p. 205
25.1 The Herzberg-Teller effect	p. 208
References	p. 209
26 REMPI spectroscopy of chlorobenzene	p. 210
26.1 Experimental details and spectrum	p. 211
26.2 Assignment	p. 212
References	p. 215
27 Spectroscopy of the chlorobenzene cation	p. 216
27.1 The X[superscript 2]B[subscript 1] state	p. 216
27.2 The B state	p. 221
References	p. 222
28 Cavity ringdown spectroscopy of the [characters not reproducible] transition in O[subscript 2]	p. 223
28.1 Experimental	p. 223
28.2 Electronic states of O[subscript 2]	p. 225
28.3 Rotational energy levels	p. 226
28.4 Nuclear spin statistics	p. 227
28.5 Spectrum assignment	p. 228
28.6 Why is this strongly forbidden transition observed?	p. 229
References	p. 229
Appendix A Units in spectroscopy	p. 230
A.1 Some fundamental constants and useful unit conversions	p. 231
Appendix B Electronic structure calculations	p. 232
B.1 Preliminaries	p. 232
B.2 Hartree-Fock method	p. 234
B.3 Semiempirical methods	p. 237
B.4 Beyond the Hartree-Fock method: allowing for electron correlation	p. 238
B.5 Density functional theory (DFT)	p. 239
B.6 Software packages	p. 240
B.7 Calculation of molecular properties	p. 240
References	p. 242
Further reading	p. 242
Appendix C Coupling of angular momenta: electronic states	p. 243
C.1 Coupling in the general case: the basics	p. 244
C.2 Coupling of angular momenta in atoms	p. 244
C.3 Coupling of electronic angular momenta in linear molecules	p. 246
C.4 Non-linear molecules	p. 248
Further reading	p. 248
Appendix D The principles of point group symmetry and group theory	p. 249
D.1 Symmetry elements and operations	p. 249
D.2 Point groups	p. 251
D.3 Classes and multiplication tables	p. 252
D.4 The matrix representation of symmetry operations	p. 254
D.5 Character tables	p. 256
D.6 Reducible representations, direct products, and direct product tables	p. 257
D.7 Cyclic and linear groups	p. 259
D.8 Symmetrized and antisymmetrized products	p. 261
Further reading	p. 261
Selected character tables	p. 262
Appendix E More on electronic configurations and electronic states: degenerate orbitals and the Pauli principle	p. 266
E.1 Atoms	p. 266
E.2 Molecules	p. 268
Appendix F Nuclear spin statistics	p. 269
F.1 Fermionic nuclei	p. 270
F.2 Bosonic nuclei	p. 270
Appendix G Coupling of angular momenta: Hund's coupling cases	p. 272
G.1 Hund's case (a)	p. 272
G.2 Hund's case (b)	p. 274
G.3 Other Hund's coupling cases	p. 276
Further reading	p. 276
Appendix H Computational simulation and analysis of rotational structure	p. 277
H.1 Calculating rotational energy levels	p. 277
H.2 Calculating transition intensities	p. 279
H.3 Determining spectroscopic constants	p. 279
References	p. 280
Further reading	p. 281
Index	p. 282

Available:*

On Order

Summary

Summary

Reviews 1

Choice Review

Table of Contents