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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