Ⅰ．Introduction 1
Ⅱ．Apparatus and Methods 3
A．Mass Spectrometric Apparatus 3
B．Apparatus Not Using Mass Analysis 9
C．Ionization Efficiency Curves 12
1．Elementary Considerations 12
2．Fine Structure in Ionization Efficiency Curves 16
3．Ionization Efficiency Curves of Negative Ions 24
D．Ionization and Appearance Potentials 26
1．Positive Ions 26
2．Negative Ions 37
E．Instrumental Factors Affecting Electron Energy 41
F．Reliability of Ionization and Appearance Potential Measurements 50
Ⅲ．Theoretical 53
A．Ionization Cross Sections 53
B．Excited Ionic States and Autoionization 54
C．Franck-Condon Principle 57
D．Ionization and Dissociation of N2 62
E．Ionization and Dissociation of Symmetrical Polyatomic Molecules 66
F．Quasi-Equilibrium Theory of Mass Spectra of Large Molecules 68
Ⅳ．Energetic Considerations 80
A．Heat of Formation of Ions 80
B．Activation Energies of Molecule-Ion Decompositions 88
C．Kinetic Energy of Ions 92
D．Ionization Potentials 105
E．Bond Strengths 128
F．Bond Strengths in Ions 141
G．Negative Ions 145
H．Heat of Dissociation of N2 and CO and the Heat of Sublimation of Carbon 152
Ⅴ．Mass Spectral Conslderations 166
A．Mass Spectra 166
1．Diatomic Molecules 166
2．Polyatomic Molecules 168
(a)Paraffins 168
(b)Olefins 174
(c)Aromatics 175
(d)Stabilities of Molecule-Ions 176
(e)Fluorocarbons 179
(f)Miscellaneous 180
B．Total Ionization 180
C．Multiply-Charged Ions 183
D．Rearrangement 185
E．Metastable Ions 194
F．Temperature Coefficients of Mass Spectra 202
G．Mass Spectra of Isotopically Substituted Molecules 204
H．Secondary Processes in the Mass Spectrometer 217
Ⅵ．Implications for Chemical Reactions 225
A．Olefin Addition Reactions 225
B．Rearrangement 229
C．Catalytic Cracking 230
D．Solvolysis of Aromatic Diazonium Salts 230
E．Aromatic Substitution 233
F．Non-Planar Ions 237
G．Charge Transfer Complexes 238
Appendix-Compilation of Critical Potential Values 239
Part 1．Positive Ions 243
Ions Containing H 243
Rare Gas Ions 244
Ions Containing B 246
Carbon and Hydrocarbon Ions 247
Ions Containing Halogens 285
Ions Containing Alkali Metal Atoms 294
Ions Containing Mg 296
Ions Containing Al 297
Ions Containing Si 297
Ions Containing P 299
Ions Containing S 299
Ions Containing Ti 301
Ions Containing V,Cr,Mn,Fe,Co,Ni 301
Ions Containing Ge 303
Ions Containing As and Sb 304
Ions Containing Se and Te 305
Ions Containing Ba 305
Ions Containing Hg 306
Ions Containing U 306
Ions of Ambiguous Composition 308
Part 2．Negative Ions 311
H Ions 311
Alkali Metal Ions 311
Ions Containing B 311
Ions Containing C 312
Ions Containing N 312
Ions Containing O 312
Ions Containing Halogen Atoms 314
Ions Containing Si 315
Ions Containing S,Se,and Te 315
Ions Containing Sb and Bi 316
Hg Ions 317
References 318
Author Index 332
Subject Index 340