Density-Functional Methods in Chemistry and Materials Science

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ISBN: 9780471967590 | 0471967599
Cover: Hardcover
Copyright: 9/9/1997

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Used in materials science, physical chemistry and physics, density functional methods provide a unifying description of electronic properties applicable to all materials while also giving specific information on the system under study. A large number of very different materials and systems (atoms, molecules, macromolecules, clusters, bulk solids, surfaces and interfaces) are presently being studied with methods based on density functional formalism. Density Functional Methods in Chemistry and Materials Science reports the results of this research. This book will be of particular interest to those research materials science from a theoretical standpoint. This work will demonstrate how the formalism has become a methodology leading to useful information on structural and electronic properties of a broad range of materials.

List of Contributors

(2)

Series Preface

xiii

(2)

Preface

1 Density-functional Formalism -- Foundations, Limitations and Applications

(18)

Michael Springborg

1.1 The Hohenberg-Kohn theorems

(3)

1.2 Kohn-Sham equations and approximate functionals

(4)

1.3 Solving the Kohn-Sham equations

(4)

1.4 Some current problems with density-functional methods

(2)

1.5 Outcomes and perspectives of density-functional calculations

(2)

References

(3)

2 Acidity and Basicity: The Role of Electronegativity, Hardness and Softness

(24)

P. Geerlings

F. De Proft

W. Langenaeker

2.1 Introduction

(1)

2.2 DFT-based properties: an overview

(2)

2.3 Computational details

(1)

2.4 Results and discussion

(15)

2.4.1 Group electronegativities, hardnesses and softnesses

(4)

2.4.2 Acidity in inorganic chemistry: bridging hydroxyl groups in zeolites

(1)

2.4.3 Acidity and basicity in organic chemistry: the role of softness

(3)

2.4.4 Two applications: the dual character of alkylgroups and the relative electron-withdrawing capacities of halogens

(7)

2.5 Conclusions

(1)

References

(4)

3 Some Recent Density-functional Studies of Molecular Systems

(26)

Michael Springborg

3.1 Introduction

(1)

3.2 Computational methods

(1)

3.3 Lengths of covalent bonds

(1)

3.4 Bond angles

(1)

3.5 Hydrogen bonds

(1)

3.6 Van der Waals bonds

(1)

3.7 Vibrations

(1)

3.8 Relative energies

(2)

3.9 Chemical reactions

(2)

3.10 Interactions with surfaces

(2)

3.11 Solvation effects

(1)

3.12 Larger systems

(1)

3.13 Electron densities

(1)

3.14 Excitations

(1)

3.15 Hyperfine coupling constants

(2)

3.16 NMR chemical shifts

(1)

3.17 Polarizabilities

(1)

3.18 NEXAFS spectra

(1)

3.19 Conclusions

(1)

References

(4)

4 Density-functional Theory as a Practical Tool in Studies of Transition Metal Chemistry and Catalysis

(36)

Tom Ziegler

4.1 Introduction

(1)

4.2 General theory and practical implementations

(2)

4.3 A validation of approximate density-functional theory

(16)

4.3.1 Bond energy calculations

(3)

4.3.2 Molecular structures

(2)

4.3.3 Energy differences of isomers and conformers

(2)

4.3.4 Electronic excitation energies and excited states

(3)

4.3.5 Ionization potentials

(2)

4.3.6 Electron affinities

(1)

4.3.7 Molecular force fields

(2)

4.3.8 Reaction profiles for elementary organic reaction steps

(1)

4.4 Applications of approximate density-functional theory to elementary reaction steps in organometallic chemistry

(9)

4.4.1 Hydroformylation

(8)

4.4.1.1 Insertion of ethylene into the cobalt-hydrogen bond

(1)

4.4.1.2 Migratory insertion of alkyl into the Co-CO bond

(3)

4.4.1.3 H(2)-induced aldehyde elimination

(3)

4.4.1.4 Dissociation of CO from HCo(CO)(4) to form the catalyst HCo(C)(3)

(1)

4.4.1.5 Concluding remarks on hydroformylation study

(1)

4.4.2 Other DFT studies on elementary reaction steps

(1)

4.5 Conclusions

(2)

References

(6)

5 Clusters - A Density-functional Story

105

(20)

R. O. Jones

5.1 Introduction

105

(3)

5.2 Transition element clusters - muffin-tin approximation

108

(1)

5.3 Density-functional calculations - LMTO method

109

(6)

5.3.1 First-row molecules H(2)-F(2)

109

(1)

5.3.2 Alkaline earth dimers

110

(1)

5.3.3 Iron series transition metal dimers

111

(2)

5.3.4 C(2), Si(2), C(3), Si(3)

113

(1)

5.3.5 O(3), S(3)

114

(1)

5.4 Density-functional calculations with simulated annealing

115

(5)

5.4.1 Sulphur and selenium clusters

116

(1)

5.4.2 Phosphorus and arsenic clusters

117

(1)

5.4.3 Aluminium and gallium clusters

118

(1)

5.4.4 Iron clusters

119

(1)

5.5 Cluster anions - structure prediction and determination

120

(2)

5.6 Conclusions

122

(1)

References

123

(2)

6 Calculations of EPR Parameters and Radical-matrix Interactions

125

(24)

Leif A. Eriksson

6.1 Introduction

125

(1)

6.2 Theoretical approach

126

(2)

6.3 Radicals in vacuum

128

(5)

6.4 Radical complexes and clusters

133

(8)

6.5 Interactions with surrounding material

141

(3)

6.6 Conclusions

144

(1)

References

144

(5)

7 Density-functional Studies of Spin-coupled Transition Metal Dimer and Tetramer Complexes

149

(40)

Louis Noodleman

Jian Li, Xin-Gui Zhao

William H. Richardson

7.1 Introduction

149

(4)

7.1.1 Metal-metal complexes

149

(1)

7.1.2 Metalloenzymes and electron transfer proteins

150

(1)

7.1.3 Structures, energetics and the catalytic cycle

150

(1)

7.1.4 Synthetic transition metal complexes as mimics

151

(1)

7.1.5 Theoretical/computational approaches -- broken symmetry

152

(1)

7.1.6 Hyperfine and EPR properties

152

(1)

7.2 Broken symmetry, spin projection and density functionals

153

(9)

7.2.1 Spin-coupling formalism for pure spin and broken symmetry

155

(2)

7.2.2 Mixed-valence systems, resonance delocalization and trapping

157

(2)

7.2.3 Spin-coupling mechanisms

159

(1)

7.2.4 Geometries and spin states

160

(1)

7.2.5 Solvation and other environmental effects

160

(1)

7.2.6 Different density functionals

161

(1)

7.3 Systems

162

(20)

7.3.1 M(2)X(9)(3-)) (M = Cr, Mo, W), (X = Cl, Br)

162

(2)

7.3.2 The diferric-oxo complex FE(III)(2)OCl(6)(2-))

164

(1)

7.3.3 Dichromium -- a spin-coupled transition metal diatomic

165

(2)

7.3.4 [Fe(2)(XXX - O)(2)](3+) dimer complexes

167

(2)

7.3.5 Broken-symmetry/spectroscopic studies of hemerythrin and hemocyanin model complexes

169

(2)

7.3.6 Exchange coupling mechanism in cuprate compounds

171

(1)

7.3.7 Biologically relevant iron-sulfur dimer and tetramer complexes

171

(5)

7.3.8 Fully delocalized mixed-valence dimer complexes

176

(1)

7.3.9 Biologically relevant manganese-oxo dimer and tetramer complexes

177

(5)

7.4 Conclusions

182

(2)

References

184

(5)

8 Calculations of Chemical Processes in Solution by Density-functional and Other Quantum-Mechanical Techniques

189

(18)

Richard P. Muller

Tomek Wesolowski

Arieh Warshel

8.1 Introduction

189

(1)

8.2 Potential energy surfaces for processes in solution

190

(5)

8.2.1 Supermolecule approaches for potential surfaces

190

(1)

8.2.2 Calculation of potential surfaces by frozen density-functional theory

191

(2)

8.2.3 Hybrid QM/MM potential surfaces

193

(2)

8.2.4 Hybrid QM/CD potential surfaces

195

(1)

8.3 Solvation-free energies of molecules and ions

195

(6)

8.3.1 Solvation-free energies using all-atom solvent models

196

(2)

8.3.1.1 Reference potentials

196

(1)

8.3.1.2 FDFT calculation of solvation-free energies

197

(1)

8.3.1.3 Solvation-free energies using point-charge representation of a solvent field

197

(1)

8.3.2 PDLD solvation-free energies

198

(1)

8.3.3 Dielectric continuum modeling of the solvation-free energy

199

(1)

8.3.4 Generalized Born solvation-free energy

200

(1)

8.3.5 `Classical' approaches for the solvation-free energy

200

(1)

8.4 Activation-free energies for chemical reactions in solution

201

(4)

8.4.1 Reference potential mapping

201

(3)

8.4.1.1 Reference potentials

201

(2)

8.4.1.2 FDFT calculations of reaction-free energies and the use of EVB reference potentials

203

(1)

8.4.1.3 Hybrid quantum-mechanical/molecular mechanics calculations of activation-free energies

203

(1)

8.4.2 Geometric mapping techniques

204

(1)

8.4.3 Potential of mean force calculations of activation-free energies

204

(1)

8.4.4 Dual-topology approaches for activation barriers

205

(1)

8.5 Conclusions

205

(1)

References

205

(2)

9 Structural and Electronic Properties of Polymeric Systems

207

(26)

Michael Springborg

9.1 Introduction

207

(2)

9.2 The first-principles method

209

(2)

9.3 Structural properties

211

(4)

9.4 Electronic properties

215

(9)

9.5 Structural defects

224

(6)

9.6 Conclusions

230

(1)

References

231

(2)

10 Electronic Structure Calculations for Crystalline Materials

233

(72)

Volker Eyert

10.1 Introduction

233

(1)

10.2 Crystalline periodicity

234

(8)

10.3 Concepts and methods

242

(7)

10.4 Metals

249

(27)

10.4.1 Simple metals

251

(8)

10.4.2 Transition metals

259

(9)

10.4.3 TaS(2)

268

(8)

10.5 Semiconductors and insulators

276

(13)

10.5.1 BaTiO(3)

276

(8)

10.5.2 V(2)O(5)

284

(5)

10.6 Magnetic materials

289

(8)

10.6.1 CrO(2)

290

(7)

10.7 Conclusions

297

(1)

References

298

(7)

11 Point Defects in Solids

305

(32)

M. J. Puska

R. M. Nieminen

11.1 Introduction

305

(2)

11.2 Density-functional theory

307

(1)

11.3 Jellium-based methods

308

(7)

11.3.1 Vacancies and voids

309

(2)

11.3.2 Atoms embedded in an electron gas

311

(4)

11.3.2.1 Scattering of electrons by impurities

312

(1)

11.3.2.2 Immersion energies

313

(1)

11.3.2.3 Screening of core holes

314

(1)

11.4 Approximate total energy models

315

(4)

11.5 First-principles calculations for point defects in solids

319

(13)

11.5.1 Vacancies and impurities in metals

322

(1)

11.5.2 Point defects in semiconductors

323

(9)

11.5.2.1 Basic electronic structure of point defects in diamond or zinc-blende structures

324

(2)

11.5.2.2 Metastability

326

(3)

11.5.2.3 Defect-formation energies

329

(3)

11.6 Conclusions

332

(1)

References

332

(5)

12 Cluster Expansions: The Link between Density-functional Methods and Alloy Thermodynamics

337

(14)

Didier de Fontaine

12.1 Introduction

337

(1)

12.2 The alloy problem

338

(1)

12.3 Cluster expansion

339

(2)

12.4 Configurational energy

341

(1)

12.5 Computation of ECIs

342

(2)

12.6 Other energy contributions

344

(3)

12.7 Conclusions

347

(1)

References

348

(3)

Index

351

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Density-Functional Methods in Chemistry and Materials Science

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