Title Details

Felice Grandinetti is professor at the Department for the Innovation in Biological Systems, Food and Forestry (DIBAF) of the University of Tuscia in Viterbo, Italy. Having obtained his academic degrees from the Sapienza University of Rome, he spent his academic and scientific career working for the Italian National Council of Research (CNR) before taking up his present appointment as Professor of General and Inorganic Chemistry at the University of Tuscia. His research activity (accounted in nearly 120 publications) is generally devoted to the experimental and theoretical study of the gas-phase chemistry of inorganic species, and is currently mainly focused on molecules and ions containing noble gas atoms.

Preface ix

Part I An Overview of Noble Gas Chemistry 1

1 A Historical Introduction 3

1.1 The Discovery of the Elements 3

1.2 The Emerging of Different Chemistries 7

1.2.1 Bulk-Phase Compounds 8

1.2.2 Molecules in Cold Matrices 11

1.2.3 Molecules in Liquid and Supercritical Noble Gases 12

1.2.4 Chemistry Under High Pressures 13

1.2.5 Gaseous Neutral Complexes 14

1.2.6 Gas-Phase Ion Chemistry 16

1.3 The Development of the Diverse Fields 18

2 Typical Compounds and Bonding Motifs 23

2.1 General Considerations 23

2.2 Clusters of Noble Gas Atoms 26

2.3 Monocoordinated Compounds 29

2.4 Dicoordinated (‘Inserted’) Compounds 30

2.5 Polycoordinated Compounds 41

2.6 Cage, Inclusion, and Adsorption Compounds 47

2.7 The Effects of the Pressure 51

3 Chemistry in Silico 55

3.1 The Role of Calculations in NobleGas Chemistry 55

3.2 Methods of Bonding Analysis 56

3.2.1 The AIM Theory 56

3.2.2 The Analysis of the ELF 57

3.2.3 The Analysis of the H(r) 58

3.2.4 The NBO Analysis 62

3.2.5 The EDA-NOCV Analysis 64

3.2.6 The Analysis of the CD Function 66

3.3 About the Performance of the Theoretical Methods 66

3.4 Illustrative Examples 70

3.4.1 Probing the Bonding Character 70

3.4.2 Structure and Stability of the XeF_n (n = 1 − 6) 84

3.4.3 Open-shell Compounds 88

3.4.4 Exploring the PES 91

3.4.5 Neutral Compounds of Helium and Neon 99

3.4.6 Novel Compounds of Argon, Krypton, and Xenon 123

3.4.7 Radon Compounds 133

3.4.8 The Aerogen Bond 138

Part II Gas-Phase Chemistry of the Noble Gases 147

4 Neutral Species 149

4.1 Complexes with Atoms and Diatomic Molecules 149

4.1.1 The Interaction Energy 149

4.1.2 The Correlation Formulas 150

4.1.3 The Ng₂ and NgNg′ 154

4.1.4 About the van der Waals Radii of the Noble Gases 157

4.1.5 The Efimov State of He₃ 159

4.1.6 Complexes with H₂, N₂, and O₂ 160

4.1.7 Complexes with C₂, CO, and CS 162

4.1.8 Complexes with the Dihalogens 166

4.1.9 Complexes with the Hydrogen Halides 173

4.1.10 Complexes with Diatomic Metal Halides 178

4.2 Complexes with Polyatomic Molecules 183

4.2.1 Complexes with CO₂, CS₂, and COS 183

4.2.2 Complexes with H₂O andNH₃ 186

4.2.3 Complexes with Hydrocarbons 191

4.2.4 Complexes with Halocarbons 194

4.2.5 Complexes with Other Organic Molecules 197

4.3 Dicoordinated Covalent Compounds 200

5 Ionic Species 203

5.1 Noble Gases as Ligands of Ionic Species 205

5.1.1 Complexes with Metal Cations 205

5.1.2 Complexes with Non-Metal Cations 220

5.1.3 Complexes with Anions 227

5.2 Protonated Noble Gases and Other Related Species 229

5.2.1 ArH⁺ as a Naturally Occurring Species 229

5.2.2 The NgH⁺ and Ng_mH_n⁺ 231

5.2.3 Complexes of the NgH⁺ with Simple Ligands 241

5.2.4 Other Noble Gas Ions of Potential Interstellar Interest 244

5.3 Noble Gas Ionic Reactions 249

5.3.1 Reactions Involving Singly-charged Cations 249

5.3.2 Reactions Involving Doubly-charged Cations 253

A Chemical Composition of Air 259

B Ab Initio and DFT Electronic Structure Methods 261

C Atomic Charges of Diatomic Molecules 269

D Bond Distances and Polarisabilities of Diatomic Molecules 271

References 273

Index 337