《ELECTRON IMPACT PHENOMENA AND THE PROPERTIES OF GASEOUS IONS》

Ⅰ．Introduction1

Ⅱ．Apparatus and Methods3

A．Mass Spectrometric Apparatus3

B．Apparatus Not Using Mass Analysis9

C．Ionization Efficiency Curves12

1．Elementary Considerations12

2．Fine Structure in Ionization Efficiency Curves16

3．Ionization Efficiency Curves of Negative Ions24

D．Ionization and Appearance Potentials26

1．Positive Ions26

2．Negative Ions37

E．Instrumental Factors Affecting Electron Energy41

F．Reliability of Ionization and Appearance Potential Measurements50

Ⅲ．Theoretical53

A．Ionization Cross Sections53

B．Excited Ionic States and Autoionization54

C．Franck-Condon Principle57

D．Ionization and Dissociation of N262

E．Ionization and Dissociation of Symmetrical Polyatomic Molecules66

F．Quasi-Equilibrium Theory of Mass Spectra of Large Molecules68

Ⅳ．Energetic Considerations80

A．Heat of Formation of Ions80

B．Activation Energies of Molecule-Ion Decompositions88

C．Kinetic Energy of Ions92

D．Ionization Potentials105

E．Bond Strengths128

F．Bond Strengths in Ions141

G．Negative Ions145

H．Heat of Dissociation of N2 and CO and the Heat of Sublimation of Carbon152

Ⅴ．Mass Spectral Conslderations166

A．Mass Spectra166

1．Diatomic Molecules166

2．Polyatomic Molecules168

(a)Paraffins168

(b)Olefins174

(c)Aromatics175

(d)Stabilities of Molecule-Ions176

(e)Fluorocarbons179

(f)Miscellaneous180

B．Total Ionization180

C．Multiply-Charged Ions183

D．Rearrangement185

E．Metastable Ions194

F．Temperature Coefficients of Mass Spectra202

G．Mass Spectra of Isotopically Substituted Molecules204

H．Secondary Processes in the Mass Spectrometer217

Ⅵ．Implications for Chemical Reactions225

A．Olefin Addition Reactions225

B．Rearrangement229

C．Catalytic Cracking230

D．Solvolysis of Aromatic Diazonium Salts230

E．Aromatic Substitution233

F．Non-Planar Ions237

G．Charge Transfer Complexes238

Appendix-Compilation of Critical Potential Values239

Part 1．Positive Ions243

Ions Containing H243

Rare Gas Ions244

Ions Containing B246

Carbon and Hydrocarbon Ions247

Ions Containing Halogens285

Ions Containing Alkali Metal Atoms294

Ions Containing Mg296

Ions Containing Al297

Ions Containing Si297

Ions Containing P299

Ions Containing S299

Ions Containing Ti301

Ions Containing V,Cr,Mn,Fe,Co,Ni301

Ions Containing Ge303

Ions Containing As and Sb304

Ions Containing Se and Te305

Ions Containing Ba305

Ions Containing Hg306

Ions Containing U306

Ions of Ambiguous Composition308

Part 2．Negative Ions311

H Ions311

Alkali Metal Ions311

Ions Containing B311

Ions Containing C312

Ions Containing N312

Ions Containing O312

Ions Containing Halogen Atoms314

Ions Containing Si315

Ions Containing S,Se,and Te315

Ions Containing Sb and Bi316

Hg Ions317

References318

Author Index332

Subject Index340