Molecules and models: the molecular structures of main group element compounds
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| Main Author: | |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Oxford [u.a.]
Oxford Univ. Press
2008
|
| Edition: | 1. publ. |
| Subjects: | |
| Online Access: | Klappentext Inhaltsverzeichnis |
| Item Description: | Includes bibliographical references and index |
| Physical Description: | XVIII, 311 S. graph. Darst. 26 cm |
| ISBN: | 9780199235353 019923535X |
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| 245 | 1 | 0 | |a Molecules and models |b the molecular structures of main group element compounds |c Arne Haaland |
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| 250 | |a 1. publ. | ||
| 264 | 1 | |a Oxford [u.a.] |b Oxford Univ. Press |c 2008 | |
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Record in the Search Index
| _version_ | 1804139111380942848 |
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| adam_text | This book provides a systematic description of the molecular structures and bonding
in simple compounds of the main group elements with particular emphasis on bond
distances, bond energies and coordination geometries. The description includes the
structures of hydrogen, halogen and methyl derivatives of the elements in each group,
some of these molecules are ionic, some polar covalent. The survey of molecules whose
structures conform to well-established trends is followed by representative examples of
molecules that do not conform. We also describe electron donor-acceptor and hydrogen
bonded complexes.
Chemists use models to systematize our knowledge, to memorize information and to
predict the structures of compounds that have not vet been studied. The book provides
a lucid discussion of a number of models such as the Lewis electron-pair bond and
the VSEPR models, the spherical and polarizable ion models, and molecular orbital
calculations, and it outlines the successes and failures of each.
Arne Haaland is a Professor of Chemistry at the University of Oslo.
‘A light and didactic reading on the structure of molecules of main-group elements. The
author has put his four decades of research experience into this book and made excellent
use of some 300 representative examples.’
Magdolna Hargittai, Hungarian Academy of Sciences
No other book brings together the analysis of molecules from normal to unusual, and
brings together so many different approaches. This book will contribute to increase our
critical understanding of molecules, which is very important.’
Odile Eisenstein, University of Montpel lier
Cover ¡нище: Rene Magritte, “l.’appcl des dines”, 1942 © R. Magritte / BONO 2008,
© Photothc4|ue R. Magritte—ADAGP, Paris 2007.
Contents
4
List of tables xv
1 Atomic properties: one-electron atoms 1
Introduction 1
1.1 A dash of physics: a particle in motion 1
1.2 A dash of physics: the forces acting between particles carrying
electric charge 2
1.3 The energies of one-electron atoms 4
1.4 The introduction of quantum mechanics: atomic orbitals
and orbital energies 6
1.5 Polar coordinates, the Bohr radius and the Rydberg energy unit 7
1.6 The energy levels of one-electron atoms 8
1.7 The orbital energy diagrams of one-electron atoms: comparison
with experiment 8
1.8 Ionization energies 9
1.9 The size of one-electron atoms 10
1.10 The ground state wavefunctions of one-electron atoms 10
1.11 Probability densities, electron densities and the shape of 15
atomic orbitals 13
1.12 The wavefunctions, probability densities and shape of 2s
atomic orbitals 14
1.13 The wavefunctions, probability densities and shape of 2p
atomic orbitals 15
1.14 The wavefunctions, probability densities and shape of 3d
atomic orbitals 16
1.15 A final dash of physics: angular momentum 18
1.16 Electron spin and spin orbitals 20
1.17 Spin-orbit coupling 22
2 Atomic properties: two-electron atoms 23
Introduction 23
2.1 The energy, the Hamiltonian operator and the wavefunctions
of a two-electron atom 23
2.2 The atomic orbital model 25
2.3 The ground state of a two-electron atom: calculation of the energy 27
2.4 Atomic size 28
2.5 First ionization energies 29
2.6 Orbital energies and Koopman’s theorem 30
2.7 The ground state of a two-electron atom: beginning the search for an
acceptable wavefunction including the electron spin 31
viii
CONTENTS
2.8 The search for acceptable wavefunctions including
the electron spin: the Pauli Principle 32
2.9 The Pauli Principle and Slater determinants 34
2.10 The lowest excited states of the helium atom: finding
acceptable wavefunctions 36
2.11 The lowest excited states of the He atom: calculation
of the energies 38
2.12 The rule of maximum spin 40
3 Atoms with more than two electrons: atomic properties
and periodic trends 41
Introduction 41
3.1 The ground state of the lithium atom 42
3.2 The beryllium atom 43
3.3 Lithium and beryllium: ionization energies and atomic sizes 43
3.4 The p-block elements from boron to neon: average configuration
energies 44
3.5 The aufbau model and the ground state electron configuration
of the elements 45
3.6 The ionization energies of the first 20 elements 46
3.7 Valence shell ¿-electron ionization energies 48
3.8 Configuration-averaged ionization energies and mean valence shell
ionization energies 48
3.9 Periodic variation of the mean valence electron shell ionization
energies of main group elements 49
3.10 The atomic sizes and bonding radii of main group elements 51
3.11 Electron affinities 52
3.12 Electronegativity and electronegativity coefficients 53
3.13 Net atomic charges and atomic dipoles 54
3.14 Atomic polarizabilities 55
References 56
4 Homonuclear diatomic molecules 57
Introduction 57
4.1 Bond strength 57
4.2 The potential energy curve 59
4.3 The equilibrium bond distance and the dissociation energy
of a diatomic molecule 59
4.4 Vibrational energy levels 60
4.5 The standard dissociation energy at zero kelvin 62
4.6 Comparison of the standard dissociation energies at 0 K and 298 K 63
4.7 Force constants 63
References 64
5 Gaseous alkali metal halides: ionic bonds 65
Introduction 65
5.1 The electric dipole moments of molecules 65
CONTENTS
ix
5.2 The spherical ion model 67
5.3 The electric dipole moments of the gaseous monomeric
alkali metal halides 68
5.4 Bond strength 69
5.5 Bond distances in alkali metal halide molecules 69
5.6 Force constants 71
5.7 The potential energy curve of a spherical ion pair 71
5.8 The dissociation energy of a spherical ion pair at zero kelvin 73
5.9 The potential energy of alkali metal halide dimers 74
5.10 Alkali metal halide dimers: calculation of equilibrium bond
distances and dissociation energies 76
5.11 Calculation of the M-X bond distance in crystalline alkali metal
halides 78
5.12 Ionic radii 80
5.13 The polarizable ion model for the monomeric alkali metal halides 81
5.14 The energy of a pair of polarized ions at infinite distance 82
5.15 The Coulomb interaction energy of two polarized ions at distance R 83
5.16 Electrides and alkalides 85
References 86
6 Other heteronuclear diatomic molecules: polar covalent bonds 87
Introduction 87
6.1 Electric dipole moments and ionic characters 87
6.2 Bond strength and bond polarity 90
6.3 Bond distances and bond polarities 92
6.4 Single bond distances in polyatomic molecules 94
6.5 A modified Schomaker-Stevenson rule for the prediction of single bond
distances between p-block elements 94
6.6 Carbon-based bonding radii 97
References 97
7 Lewis’ “cubical atom” model. Molecular orbital calculations on the
one-electron molecule and the two-electron molecule H2 99
Introduction 99
7.1 The electron octet, the “cubical atom,” and the electron pair bond 99
7.2 Molecular orbitals: the hydrogen molecule ion, Hj 102
7.3 Approximate molecular orbitals obtained by linear combinations
of atomic orbitals 105
7.4 Improvement of the LCAO MO 108
7.5 The hydrogen molecule and the molecular orbital approximation 109
7.6 The electric dipole moment of HD: failure of the Born-Oppenheimer
(adiabatic) approximation 112
References 113
X
CONTENTS
$ Molecular orbital calculations on heteronuclear diatomic
molecules, hybridization, and estimation of
net atomic charges from calculated
electron densities 115
Introduction 115
8.1 The LiH molecule: approximate molecular orbital calculations 115
8.2 Simplified Hiickel calculations 119
8.3 The importance of the “resonance integral”, H 2 121
8.4 A more accurate MO calculation for LiH 122
8.5 Hybrid atomic orbitals 123
8.6 Hybridization energies 126
8.7 Orthogonal hybrid orbitals 127
8.8 Equivalent hybrid orbitals 128
8.9 The estimation of net atomic charges from calculated electron
densities 129
References 133
9 Homonuclear diatomic species of second-period elements from LÎ2 to Ne2 135
Introduction 135
9.1 The dilithium molecule 135
9.2 The beryllium dimer 136
9.3 The diboron molecule 137
9.4 The dicarbon and dinitrogen molecules 139
9.5 The dioxygen and difiourine molecules 139
9.6 A molecular orbital energy level diagram for the species
from Li 2 to Ne2 140
9.7 The long-range attraction between neon atoms 141
9.8 The helium dimer 144
9.9 van der Waals interactions: dipole-dipole interactions;
dipole-induced dipole interactions; and dispersion interactions 144
9.10 van der Waals radii from crystal structures 145
9.11 The crystal structure of chlorine 147
9.12 The liquid structures of neon and methane 147
References 148
10 Structure and bonding in the gaseous dihalides and dialkyl
derivatives of the Group 2 and Group 12 metals 149
Introduction 149
10.1 Are the gaseous dihalides of the Group 2 and 12 halides linear? 149
10.2 Molecular shapes 152
10.3 Bond distances in metal dichlorides 152
10.4 Bond energies of metal dichlorides 153
10.5 The spherical ion model and the mean bond energies of the
Group 2 and 12 metal dichlorides 155
10.6 The polarizable ion model and the shape of the heavier Group 2
metal halides 156
10.7 The Valence Shell Electron Pair Repulsion (VSEPR) model 157
CONTENTS xi
10.8 The VSEPR model and the structures of the Group 2 and 12
metal dihalides 157
10.9 The hybridization model and two-center molecular orbitals 158
10.10 Delocalized molecular orbitals 160
10.11 Metal dialkyls and dihydrides 162
10.12 Group variation of bond distances 163
References 164
11 Structure and bonding in the gaseous monochlorides,
trichlorides and trimethyl derivatives of the
Group 13 elements 167
Introduction 167
11.1 Mono- and tri-chlorides of the Group 13 elements 167
11.2 The molecular structures of the monomeric trichlorides 168
11.3 Trimethylderivatives of the Group 13 elements 168
11.4 Group variation of M-C and M-Cl bond distances and
bond energies 169
11.5 The spherical ion model and the bond energies of the
Group 13 element chlorides 170
11.6 The Valence Shell Electron Pair Repulsion model 170
11.7 sp2 hybridization and localized molecular orbitals 171
11.8 The relative stabilities of the Lewis-valent and subvalent
chlorides 174
References 176
12 Electron deficient molecules: three-center, two-electron bonds 177
Introduction 177
12.1 The trihydrogen cation 177
12.2 A molecular orbital description of 177
12.3 Jahn-Teller distortion 180
12.4 The first electron deficient molecule, diborane 181
12.5 Hexamethyldialane: bridging methyl groups 183
12.6 Comparison of the strength of hydrogen, methyl and
phenyl bridges 183
12.7 Nuclear magnetic resonance spectroscopy and bridge-terminal
exchange of methyl groups in (CH3)4Al2(|x-CH3)2 184
12.8 Clusters 187
12.9 Cage compounds: closoboranes and carboranes 188
12.10 The dimethylberyllium polymer and the methyllithium
tetramer 189
References 191
13 Structure and bonding in simple compounds of the
Group 14 elements 193
Introduction 193
13.1 The structures of the subvalent element chlorides 194
13.2 Bonding models for the subvalent element chlorides 194
CONTENTS
xii
13.3 The structures of the Lewis-valent element chlorides
13.4 Hydrogen and methyl derivatives of the Lewis-valent elements
13.5 Bonding models for tetravalent compounds
13.6 Construction of two orthogonal and equivalent hybrid orbitals
spanning an arbitrary valence angle ß
13.7 Radical species formed by H atom extraction from methane
13.8 Heteroleptic compounds: the molecular structures of fluorinated
methanes and methylsilanes
13.9 C-F and C-H bond energies in fluorinated methanes
13.10 The polarity of C-F bonds in fluorinated methanes
13.11 The polarity of Si-F and Si-C bonds in fluorinated methylsilanes
13.12 The effect of introducing more electronegative atoms at the
most electronegative of two bonded atoms
13.13 Inductive versus steric effects
References
14 Structure and bonding in some simple hydrocarbons
and in ethane and ethene analogues
of the heavier Group 14 elements
Introduction
14.1 The molecular structures of ethane, ethene, and ethyne
14.2 Ethane, ethene, and ethyne: model considerations
14.3 Single C-C bond distances and hybridization
14.4 Delocalized tc orbitals in benzene
14.5 Ethane analogues of the heavier Group 14 elements
14.6 The molecular structures of ethene analogues of the
heavier Group 14 elements
14.7 Molecular orbital descriptions of the ethene analogues of the
heavier Group 14 elements
14.8 The molecular structure of S12H2
References
15 Structure and bonding in simple compounds of the
Group 15 elements
Introduction
15.1 Compounds of Lewis-valent elements
15.2 Inversion of the N atom in ammonia
15.3 Some planar amines
15.4 The gas phase molecular structures of phosphorus
pen tail uoride and pentachloride
15.5 The solid state structures of the phosphorus pentahalides
15.6 Other homoleptic derivatives of hypervalent Group 15 elements
15.7 The strength of the hypervalent bonds
15.8 The pentaphenyl derivatives of Group 15 elements
15.9 Structural non-rigidity and Berry pseudorotation
15.10 Pentacoordination and the VSEPR model
15.11 Heteroleptic hypervalent compounds
195
196
196
198
199
200
203
204
205
206
207
208
209
209
209
211
213
214
216
217
220
222
223
225
225
225
227
228
230
231
232
233
234
235
236
236
CONTENTS xiii
15.12 Molecular orbital descriptions of the hypervalent compounds 238
References 240
16 Electron donor—acceptor complexes 241
Introduction 241
16.1 Covalent and dative bonds 242
16.2 N— B bond distances and dissociation energies in substituted
amine borane complexes 243
16.3 Complexes of the electron donors HCN and H3CCN with the
electron acceptor BF3 244
16.4 Some complexes of trimethylaluminum 245
16.5 Two complexes containing dative and covalent bond distances
between identical atom pairs 246
16.6 Dative bonds and the VSEPR model 247
16.7 The molecular structure of (Me3N)2AlCl3, a complex with
two dative bonds 249
16.8 Bridge bonds: bonds with equal covalent and dative contributions 250
16.9 Triple bridges and cage compounds 251
16.10 Dative tv-bonding 252
16.11 Some complexes of beryllium, zinc and silicon 253
16.12 Electron donor-acceptor complexes with Group 15 acceptor atoms 253
References 255
17 Structure and bonding in simple compounds
of the Group 16 elements 257
Introduction 257
17.1 Compounds of the Lewis-valent elements 257
17.2 Across angle radii 258
17.3 MO description of bonding in the Lewis-valent compounds 260
17.4 Ions and radicals formed from H2O 261
17.5 The molecular structure of hydrogen peroxide, HOOH 261
17.6 The peculiar structure of dioxygen difiuoride, FOOF: anomeric
delocalization 263
17.7 The molecular structures of compounds of hypervalent Group 14 elements 264
17.8 Compounds of hypervalent Group 16 elements: model considerations 266
17.9 The solid state structure of tellurium tetrachloride 268
References 269
18 Structure and bonding in simple compounds of the Group 17 elements 271
Introduction 271
18.1 Compounds of Lewis-valent halogens 271
18.2 Compounds of hypervalent halogens 272
18.3 Compounds of hypervalent halogens: model considerations 274
18.4 The crystal structure of iodine trichloride 275
18.5 19F NMR spectra of CIF3 and BrF3 276
18.6 Some electron donor-acceptor complexes of dihalogens 276
18.7 Hydrogen bonded complexes 279
xiv
CONTENTS
18.8 The structures of ice and liquid water 281
18.9 Poly water 282
References 284
19 Structure and bonding in simple compounds of the noble gases 285
Introduction 285
19.1 Hypervalent compounds of the noble gases 285
19.2 Two compounds of Xe+ 287
References 287
20 Structure and bonding in oxides and oxoacids of carbon, sulfur,
nitrogen, phosphorus, and chlorine 289
Introduction 289
20.1 Carbon oxides 289
20.2 Some sulfur oxides 291
20.3 Sulfur oxofluorides 293
20.4 Sulfuric acid and related compounds 294
20.5 Mono-nitrogen oxides and their N-N bonded dimers 295
20.6 Hartree—Fock and configuration interaction calculations
on ONNO and 02NN02 298
20.7 Nitric acid and nitric acid anhydride (N2O5) 299
20.8 Dinitrogen monoxide 299
20.9 Phosphorus oxides 300
20.10 The crystal structure of orthophosphoric acid 302
20.11 Chlorine oxides and perchloric acid 303
20.12 The shape of triatomic molecules formed from elements in
Groups 14 to 18 304
References 305
Index
307
|
| any_adam_object | 1 |
| author | Haaland, Arne |
| author_GND | (DE-588)1026812526 |
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| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Physik Chemie |
| edition | 1. publ. |
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| genre | (DE-588)4123623-3 Lehrbuch gnd-content |
| genre_facet | Lehrbuch |
| id | DE-604.BV035495186 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T21:38:53Z |
| institution | BVB |
| isbn | 9780199235353 019923535X |
| language | English |
| lccn | 2007040778 |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-017551510 |
| oclc_num | 173809048 |
| open_access_boolean | |
| owner | DE-91G DE-BY-TUM DE-11 DE-703 |
| owner_facet | DE-91G DE-BY-TUM DE-11 DE-703 |
| physical | XVIII, 311 S. graph. Darst. 26 cm |
| publishDate | 2008 |
| publishDateSearch | 2008 |
| publishDateSort | 2008 |
| publisher | Oxford Univ. Press |
| record_format | marc |
| spelling | Haaland, Arne Verfasser (DE-588)1026812526 aut Molecules and models the molecular structures of main group element compounds Arne Haaland Molecules & models 1. publ. Oxford [u.a.] Oxford Univ. Press 2008 XVIII, 311 S. graph. Darst. 26 cm txt rdacontent n rdamedia nc rdacarrier Includes bibliographical references and index Molecular structure Molecules Models Molekülstruktur (DE-588)4170383-2 gnd rswk-swf Hauptgruppenelement (DE-588)4122190-4 gnd rswk-swf Chemische Bindung (DE-588)4009843-6 gnd rswk-swf Molekülorbital (DE-588)4127526-3 gnd rswk-swf (DE-588)4123623-3 Lehrbuch gnd-content Molekülstruktur (DE-588)4170383-2 s Chemische Bindung (DE-588)4009843-6 s Molekülorbital (DE-588)4127526-3 s Hauptgruppenelement (DE-588)4122190-4 s DE-604 Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017551510&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Klappentext Digitalisierung UB Bayreuth - ADAM Catalogue Enrichment application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017551510&sequence=000002&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Haaland, Arne Molecules and models the molecular structures of main group element compounds Molecular structure Molecules Models Molekülstruktur (DE-588)4170383-2 gnd Hauptgruppenelement (DE-588)4122190-4 gnd Chemische Bindung (DE-588)4009843-6 gnd Molekülorbital (DE-588)4127526-3 gnd |
| subject_GND | (DE-588)4170383-2 (DE-588)4122190-4 (DE-588)4009843-6 (DE-588)4127526-3 (DE-588)4123623-3 |
| title | Molecules and models the molecular structures of main group element compounds |
| title_alt | Molecules & models |
| title_auth | Molecules and models the molecular structures of main group element compounds |
| title_exact_search | Molecules and models the molecular structures of main group element compounds |
| title_full | Molecules and models the molecular structures of main group element compounds Arne Haaland |
| title_fullStr | Molecules and models the molecular structures of main group element compounds Arne Haaland |
| title_full_unstemmed | Molecules and models the molecular structures of main group element compounds Arne Haaland |
| title_short | Molecules and models |
| title_sort | molecules and models the molecular structures of main group element compounds |
| title_sub | the molecular structures of main group element compounds |
| topic | Molecular structure Molecules Models Molekülstruktur (DE-588)4170383-2 gnd Hauptgruppenelement (DE-588)4122190-4 gnd Chemische Bindung (DE-588)4009843-6 gnd Molekülorbital (DE-588)4127526-3 gnd |
| topic_facet | Molecular structure Molecules Models Molekülstruktur Hauptgruppenelement Chemische Bindung Molekülorbital Lehrbuch |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017551510&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=017551510&sequence=000002&line_number=0002&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT haalandarne moleculesandmodelsthemolecularstructuresofmaingroupelementcompounds AT haalandarne moleculesmodels |