Calculation of NMR and EPR parameters : theory and applications / [edited by] Martin Kaupp, Vladimir G. Malkin , Michael Bühl.

Format:

Book

Contributor:

Kaupp, Martin.

Malkin, Vladimir G.

Bühl, Michael.

Language:

English

Subjects (All):

Nuclear magnetic resonance spectroscopy.

Electron paramagnetic resonance spectroscopy.

Quantum chemistry.

Physical Description:

xviii, 603 pages : illustrations ; 25 cm

Place of Publication:

Weinheim : Wiley-VCH, 2004.

Contents:

1 Introduction: The Quantum Chemical Calculation of NMR and EPR Parameters / Martin Kaupp, Michael Buhl, Vladimir G. Malkin 3

2 Theory of NMR parameters. From Ramsey to Relativity, 1953 to 1983 / Pekka Pyykko 7

2.2 Spin-Spin Coupling 9

2.3 Chemical Shifts 11

2.4 General Aspects 13

2.5 From 1983 to 2003 15

3 Historical Aspects of EPR Parameter Calculations / Frank Neese, Marketa L. Munzarova 21

4 The Effective Spin Hamiltonian Concept from a Quantum Chemical Perspective / Gerald H. Lushington 33

5 Fundamentals of Nonrelativistic and Relativistic Theory of NMR and EPR Parameters / Werner Kutzelnigg 43

5.2 Classical Theory of the Interaction of a Charged Particle with an Electromagnetic Field 44

5.3 Quantum Mechanical Hamiltonians in a Time-Independent Electromagnetic Field 50

5.4 Perturbation Theory of Magnetic Effects 58

5.5 Non-Relativistic Theory of EPR and NMR Parameters 62

5.6 Relativistic Theory of Magnetic Properties 69

5.7 The Leading Relativistic Corrections 72

Part B NMR Parameters, Methodological Aspects

6 Chemical Shifts with Hartree-Fock and Density Functional Methods / Christoph van Wullen 85

6.2 Linear Response and the Gauge Origin Problem 88

6.3 Determination of the First-Order Orbitals 90

6.4 Distributed Gauge Origins, IGLO and GIAO Approaches 92

6.5 Distributed Gauge Origins in Real Space, a "Continuous Set of Gauge Transformations" 96

6.6 Beyond Pure Density Functional Theory 97

7 Spin-Spin Coupling Constants with HF and DFT Methods / Trygve Helgaker, Magdalena Pecul 101

7.2 The Calculation of Indirect Nuclear Spin-Spin Coupling Constants 102

7.3 Examples of Applications 115

8 Electron-Correlated Methods for the Calculation of NMR Chemical Shifts / Jurgen Gauss, John F. Stanton 123

8.2 Theoretical Background 125

8.3 Electron-Correlated Treatment of NMR Chemical Shifts 132

8.4 Special developments 133

8.5 Numerical Results 134

9 Semiempirical Methods for the Calculation of NMR Chemical Shifts / Thomas Heine, Gotthard Seifert 141

9.2 Methods 142

9.3 Representative Applications 147

9.4 Concluding Remarks: Limitations of Semiempirical Methods for the Calculation of NMR Parameters 151

10 Ro-Vibrational Corrections to NMR Parameters / Torgeir A. Ruden, Kenneth Ruud 153

10.2 Perturbation Theory 154

10.3 Other Approaches for Calculating Vibrationally Averaged NMR Properties 163

10.4 Examples of Vibrational Contributions to NMR Properties 164

11 Molecular Dynamics and NMR Parameter Calculations / Debra J. Searles, Hanspeter Huber 175

11.2 Methods 176

12 Use of Continuum Solvent Models in Magnetic Resonance Parameter Calculations / Ilaria Ciofini 191

12.2 General Features of Continuum Models 192

12.3 Applications of Continuum Models to the Prediction of NMR Parameters 197

12.4 Applications of Continuum Models to the Prediction of EPR Parameters 201

13 Perturbational and ECP Calculation of Relativistic Effects in NMR Shielding and Spin-Spin Coupling / Juha Vaara, Pekka Manninen, Perttu Lantto 209

13.2 Nuclear Shielding and Spin-Spin Coupling 210

13.3 Electronic Hamiltonian 211

13.4 Non-Relativistic Contributions 212

13.5 Relativistic Kinematics and the Spin-Zeeman Effect 213

13.6 Spin-Orbit Coupling 216

13.7 Relativistic Corrections to Shielding and Coupling 217

14 Calculation of Heavy-Nucleus Chemical Shifts. Relativistic All-Electron Methods / Jochen Autschbach 227

15 Relativistic Calculations of Spin-Spin Coupling Constants of Heavy Nuclei / Jochen Autschbach, Tom Ziegler 249

15.2 Methodological Aspects 251

15.3 Computational Results 253

16 Calculations of Magnetic Resonance Parameters in Solids and Liquids Using Periodic Boundary Conditions / Chris J. Pickard, Francesco Mauri 265

16.2 Cluster Approaches to Extended Systems 265

16.3 The Limitations of the Cluster Approach 266

16.4 Infinite Crystals, Periodic Boundary Conditions 267

16.5 Magnetic Resonance Parameters within Periodic Boundary Conditions 267

16.6 Applications of the Planewave-GIPAW Method 272

16.7 Work in Progress and Future Challenges 275

17 Calculation of Nuclear Quadrupole Coupling Constants / Peter Schwerdtfeger, Markus Pernpointner, Witold Nazarewicz 279

17.2 Nuclear Quadrupole Moments 282

17.3 Field Gradients from Ab Initio Calculations 285

17.4 Field Gradients from Density Functional Calculations 288

18 Interpretation of NMR Chemical Shifts / Martin Kaupp 293

18.2 Nonrelativistic Case 295

18.3 Relativistic Effects 302

19 Interpretation of Indirect Nuclear Spin-Spin Coupling Constants / Olga L. Malkina 307

19.2 The Dirac Vector Model of Spin-Spin Coupling 309

19.3 Decomposition into Individual Contributions 310

19.4 Visualization of Coupling by Real-Space Functions 318

20 First-Principles Calculations of Paramagnetic NMR Shifts / Seongho Moon, Serguei Patchkovskii 325

20.2 Paramagnetic Shielding Tensor: The General Case Treatment 326

20.3 Paramagnetic Shielding for an Isolated Kramers Doublet State 330

20.4 Practical Applications 333

Part C NMR Parameters, Applications

21 NMR Parameters in Proteins and Nucleic Acids / David A. Case 341

21.2 Chemical Shifts, Classical Models 342

21.3 Chemical Shifts Calculations on Polypeptides and Proteins 345

21.4 Chemical Shifts in Nucleic Acids 346

21.5 Indirect Spin-Spin Couplings in Biomolecules 347

22 Characterizing Two-Bond NMR [superscript 13]C-[superscript 15]N, [superscript 15]N-[superscript 15]N, and [superscript 19]F-[superscript 15]N Spin-Spin Coupling Constants across Hydrogen Bonds Using Ab Initio EOM-CCSD Calculations / Janet E. Del Bene 353

23 Calculation of NMR Parameters in Carbocation Chemistry / Hans-Ullrich Siehl, Valerije Vrcek 371

23.2 Alkyl and Cycloalkyl Cations 372

23.3 Bicyclic and Polycyclic Carbocations 379

23.4 Vinyl Cations 382

23.5 [pi]-Stabilized Carbocations 384

23.6 Heteroatom Stabilized Carbocations 388

24 Aromaticity Indices from Magnetic Shieldings / Zhongfang Chen, Thomas Heine, Paul v. R. Schleyer, Dage Sundholm 395

24.2 An Overview of Aromaticity Indices Based on Magnetic Shielding 395

24.3 Applications 401

25 Fullerenes / Thomas Heine 409

25.2 Efficient Computation of NMR Parameters of Fullerenes and Their Derivatives 410

25.3 Classical IPR Fullerenes 411

25.4 [superscript 13]C NMR Spectra of Isomeric Fullerene Addition Compounds 413

25.5 Endohedral Fullerenes 414

25.6 Fullerene Dimers and Dimer-like Compounds 416

25.7 Solid State NMR of Fullerenes 418

26 NMR of Transition Metal Compounds / Michael Buhl 421

26.2 Ligand Chemical Shifts 422

26.3 Metal Chemical Shifts 424

26.4 Spin-Spin Coupling Constants 427

27 Characterization of NMR Tensors via Experiment and Theory / Roderick E. Wasylishen 433

27.2 Magnetic Shielding and Chemical Shifts 434

27.3 Nuclear Spin-Spin Coupling 439

27.4 NMR Spectra of Quadrupolar Nuclei in Solids 443

28 Calculations of Nuclear Magnetic Resonance Parameters in Zeolites / Annick Goursot, Dorothee Berthomieu 449

28.2 Theoretical Methods 451

28.3 NMR of Framework Elements: Structure Characterization 453

28.4 [superscript 1]H NMR: Acidity and Proton Transfer 455

28.5 NMR Studies of Guest Molecules in Zeolites: in situ NMR 457

Part D EPR Parameters, Methodological Aspects

29 DFT Calculations of EPR Hyperfine Coupling Tensors / Marketa L. Munzarova 463

29.2 Theoretical Background 464

29.3 The Performance of the Model 467

30 Ab Initio Post-Hartree-Fock Calculations of Hyperfine Coupling Tensors and Their Comparison with DFT Approaches / Bernd Engels 483

30.2 Problems Appearing in MR-CI Computations of A[subscript iso] 485

30.3 Error Cancellations in Computations of A[subscript iso] with DFT 489

31 Alternative Fermi Contact Operators for EPR and NMR / Vitaly A. Rassolov, Daniel M.

Chipman 493

31.2 Derivation of New Alternative Operators 494

31.3 Formal Properties of Short-Range Alternative Operators 496

31.4 EPR Calculations 499

31.5 NMR Calculations 501

32 Calculation of EPR g-Tensors with Density Functional Theory / Serguei Patchkovskii, Georg Schreckenbach 505

32.2 The Physical Origin of the g-Tensor 506

32.3 DFT Expressions for g-Tensors of Isolated Molecules 508

32.4 Numerical Performance of the DFT Approaches 519

33 Ab Initio Calculations of g-Tensors / Gerald H. Lushington 533

34 Zero-Field Splitting / Frank Neese 541

34.2 Zero-Field Splittings in EPR Spectroscopy 542

34.3 Theory of Zero-Field Splittings 552

34.4 Calculation of Zero-Field Splittings 557

Part E EPR Parameters, Applications

35 Computation of Hyperfine Coupling Tensors to Complement EPR Experiments / Fuqiang Ban, James W. Gauld, Russell J. Boyd 567

35.2 Insight Gained from a Conventional Ab Initio Approach 568

35.3 Benchmark Results Using Conventional Methods on Static Gas-phase Structures 568

35.4 The Performance of Contracted Pople Basis Sets for Small Radicals Consisting Only of First-Row Atoms 570

35.5 Density Functional Theory: An Alternative to a Conventional Ab Initio Approach 571

35.6 Consideration of Environmental Effects 572

35.7 Illustration of the Applications of DFT Methods to Biological Radicals 574

36 Applications to EPR in Bioinorganic Chemistry / Frank Neese 581

36.2 Biological Metal Sites 582.

ISBN:

3527307796

OCLC:

56436158