Calculation of NMR and EPR parameters : theory and applications

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Weinheim : Wiley-VCH, 2004

ISBN:

9783527307791

Subject Term:

Nuclear magnetic resonance spectroscopy

Electron paramagnetic resonance spectroscopy

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Library	Item Barcode	Call Number	Material Type	Item Category 1	Status
Searching... PSZ JB	30000010070105	QD96.N8 C34 2004	Open Access Book	Book	Searching... Unknown
Searching... PSZ KL	30000010080498	QD96.N8 C34 2004	Open Access Book	Book	Searching... Unknown

This is the first book to present the necessary quantum chemical methods for both resonance types in one handy volume, emphasizing the crucial interrelation between NMR and EPR parameters from a computational and theoretical point of view.
Here, readers are given a broad overview of all the pertinent topics, such as basic theory, methodic considerations, benchmark results and applications for both spectroscopy methods in such fields as biochemistry, bioinorganic chemistry as well as with different substance classes, including fullerenes, zeolites and transition metal compounds. The chapters have been written by leading experts in a given area, but with a wider audience in mind.
The result is the standard reference on the topic, serving as a guide to the best computational methods for any given problem, and is thus an indispensable tool for scientists using quantum chemical calculations of NMR and EPR parameters.
A must-have for all chemists, physicists, biologists and materials scientists who wish to augment their research by quantum chemical calculations of magnetic resonance data, but who are not necessarily specialists in these methods or their applications. Furthermore, specialists in one of the subdomains of this wide field will be grateful to find here an overview of what lies beyond their own area of focus.

Author Notes

Martin Kaupp is Professor at the Institut fur Anorganische Chemie at Universitat Wurzburg
Michael Buhl is Research Associate in the Theoretical Department of the Max-Planck-Institut fur Kohlenforschung in Mulheim/Ruhr (Germany) and lecturer at the University of Wuppertal
Vladimir G. Malkin is a Leading Research Scientist at the Institute of Inorganic Chemistry of the Slovak Academy of Sciences (Bratislava, Slovak Republic)

Martin Kaupp and Michael Buhl and Vladimir G. MalkinPekka PyykkoFrank Neese and Marketa L. MunzarovaGerald H. LushingtonWerner KutzelniggChristoph van WullenTrygve Helgaker and Magdalena PeculJurgen Gauss and John F. StantonThomas Heine and Gotthard SeifertTorgeir A. Ruden and Kenneth RuudDebra J. Searles and Hanspeter HuberIlaria CiofiniJuha Vaara and Pekka Manninen and Perttu LanttoJochen AutschbachJochen Autschbach and Tom ZieglerChris J. Pickard and Francesco MauriPeter Schwerdtfeger and Markus Pernpointner and Witold NazarewiczMartin KauppOlga L. MalkinaSeongho Moon and Serguei PatchkovskiiDavid A. CaseJanet E. Del BeneHans-Ullrich Siehl and Valerije VrcekZhongfang Chen and Thomas Heine and Paul v. R. Schleyer and Dage SundholmThomas HeineMichael BuhlRoderick E. WasylishenAnnick Goursot and Dorothee BerthomieuMarketa L. MunzarovaBernd EngelsVitaly A. Rassolov and Daniel M. ChipmanSerguei Patchkovskii and Georg SchreckenbachGerald H. LushingtonFrank NeeseFuqiang Ban and James W. Gauld and Russell J. BoydFrank Neese

Foreword	p. XIII
List of Contributors	p. XV
Part A Introductory Chapters
1 Introduction: The Quantum Chemical Calculation of NMR and EPR Parameters	p. 3
2 Theory of NMR parameters. From Ramsey to Relativity, 1953 to 1983	p. 7
2.1 Introduction	p. 7
2.2 Spin-Spin Coupling	p. 9
2.3 Chemical Shifts	p. 11
2.4 General Aspects	p. 13
2.5 From 1983 to 2003	p. 15
3 Historical Aspects of EPR Parameter Calculations	p. 21
4 The Effective Spin Hamiltonian Concept from a Quantum Chemical Perspective	p. 33
5 Fundamentals of Nonrelativistic and Relativistic Theory of NMR and EPR Parameters	p. 43
5.1 Introduction	p. 43
5.2 Classical Theory of the Interaction of a Charged Particle with an Electromagnetic Field	p. 44
5.3 Quantum Mechanical Hamiltonians in a Time-Independent Electromagnetic Field	p. 50
5.4 Perturbation Theory of Magnetic Effects	p. 58
5.5 Non-Relativistic Theory of EPR and NMR Parameters	p. 62
5.6 Relativistic Theory of Magnetic Properties	p. 69
5.7 The Leading Relativistic Corrections	p. 72
5.8 Concluding Remarks	p. 81
Part B NMR Parameters, Methodological Aspects
6 Chemical Shifts with Hartree-Fock and Density Functional Methods	p. 85
6.1 Introduction	p. 85
6.2 Linear Response and the Gauge Origin Problem	p. 88
6.3 Determination of the First-Order Orbitals	p. 90
6.4 Distributed Gauge Origins, IGLO and GIAO Approaches	p. 92
6.5 Distributed Gauge Origins in Real Space, a "Continuous Set of Gauge Transformations"	p. 96
6.6 Beyond Pure Density Functional Theory	p. 97
6.7 Conclusions	p. 99
7 Spin-Spin Coupling Constants with HF and DFT Methods	p. 101
7.1 Introduction	p. 101
7.2 The Calculation of Indirect Nuclear Spin-Spin Coupling Constants	p. 102
7.3 Examples of Applications	p. 115
7.4 Conclusions	p. 119
8 Electron-Correlated Methods for the Calculation of NMR Chemical Shifts	p. 123
8.1 Introduction	p. 123
8.2 Theoretical Background	p. 125
8.3 Electron-Correlated Treatment of NMR Chemical Shifts	p. 132
8.4 Special developments	p. 133
8.5 Numerical Results	p. 134
8.6 Summary and Outlook	p. 136
9 Semiempirical Methods for the Calculation of NMR Chemical Shifts	p. 141
9.1 Introduction	p. 141
9.2 Methods	p. 142
9.3 Representative Applications	p. 147
9.4 Concluding Remarks: Limitations of Semiempirical Methods for the Calculation of NMR Parameters	p. 151
10 Ro-Vibrational Corrections to NMR Parameters	p. 153
10.1 Introduction	p. 153
10.2 Perturbation Theory	p. 154
10.3 Other Approaches for Calculating Vibrationally Averaged NMR Properties	p. 163
10.4 Examples of Vibrational Contributions to NMR Properties	p. 164
10.5 Summary	p. 171
11 Molecular Dynamics and NMR Parameter Calculations	p. 175
11.1 Introduction	p. 175
11.2 Methods	p. 176
11.3 Examples	p. 182
11.4 Summary and Conclusions	p. 187
12 Use of Continuum Solvent Models in Magnetic Resonance Parameter Calculations	p. 191
12.1 Introduction	p. 191
12.2 General Features of Continuum Models	p. 192
12.3 Applications of Continuum Models to the Prediction of NMR Parameters	p. 197
12.4 Applications of Continuum Models to the Prediction of EPR Parameters	p. 201
12.5 Conclusions	p. 205
13 Perturbational and ECP Calculation of Relativistic Effects in NMR Shielding and Spin-Spin Coupling	p. 209
13.1 Introduction	p. 209
13.2 Nuclear Shielding and Spin-Spin Coupling	p. 210
13.3 Electronic Hamiltonian	p. 211
13.4 Non-Relativistic Contributions	p. 212
13.5 Relativistic Kinematics and the Spin-Zeeman Effect	p. 213
13.6 Spin-Orbit Coupling	p. 216
13.7 Relativistic Corrections to Shielding and Coupling	p. 217
13.8 Conclusions	p. 223
14 Calculation of Heavy-Nucleus Chemical Shifts. Relativistic All-Electron Methods	p. 227
14.1 Introduction	p. 227
14.2 Methodological Aspects	p. 229
14.3 Computational Results	p. 234
14.4 Summary	p. 244
15 Relativistic Calculations of Spin-Spin Coupling Constants of Heavy Nuclei	p. 249
15.1 Introduction	p. 249
15.2 Methodological Aspects	p. 251
15.3 Computational Results	p. 253
15.4 Summary	p. 262
16 Calculations of Magnetic Resonance Parameters in Solids and Liquids Using Periodic Boundary Conditions	p. 265
16.1 Introduction	p. 265
16.2 Cluster Approaches to Extended Systems	p. 265
16.3 The Limitations of the Cluster Approach	p. 266
16.4 Infinite Crystals, Periodic Boundary Conditions	p. 267
16.5 Magnetic Resonance Parameters within Periodic Boundary Conditions	p. 267
16.6 Applications of the Planewave-GIPAW Method	p. 272
16.7 Work in Progress and Future Challenges	p. 275
16.8 Conclusion	p. 276
17 Calculation of Nuclear Quadrupole Coupling Constants	p. 279
17.1 Introduction	p. 279
17.2 Nuclear Quadrupole Moments	p. 282
17.3 Field Gradients from Ab Initio Calculations	p. 285
17.4 Field Gradients from Density Functional Calculations	p. 288
18 Interpretation of NMR Chemical Shifts	p. 293
18.1 Introduction	p. 293
18.2 Nonrelativistic Case	p. 295
18.3 Relativistic Effects	p. 302
18.4 Concluding Remarks	p. 305
19 Interpretation of Indirect Nuclear Spin-Spin Coupling Constants	p. 307
19.1 Introduction	p. 307
19.2 The Dirac Vector Model of Spin-Spin Coupling	p. 309
19.3 Decomposition into Individual Contributions	p. 310
19.4 Visualization of Coupling by Real-Space Functions	p. 318
19.5 Conclusions	p. 323
20 First-Principles Calculations of Paramagnetic NMR Shifts	p. 325
20.1 Introduction	p. 325
20.2 Paramagnetic Shielding Tensor: The General Case Treatment	p. 326
20.3 Paramagnetic Shielding for an Isolated Kramers Doublet State	p. 330
20.4 Practical Applications	p. 333
20.5 Conclusions	p. 337
Part C NMR Parameters, Applications
21 NMR Parameters in Proteins and Nucleic Acids	p. 341
21.1 Introduction	p. 341
21.2 Chemical Shifts, Classical Models	p. 342
21.3 Chemical Shifts Calculations on Polypeptides and Proteins	p. 345
21.4 Chemical Shifts in Nucleic Acids	p. 346
21.5 Indirect Spin-Spin Couplings in Biomolecules	p. 347
21.6 Conclusions	p. 349
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	p. 353
22.1 Introduction	p. 353
22.2 Methods	p. 354
22.3 Discussion	p. 355
22.4 Concluding Remarks	p. 369
23 Calculation of NMR Parameters in Carbocation Chemistry	p. 371
23.1 Introduction	p. 371
23.2 Alkyl and Cycloalkyl Cations	p. 372
23.3 Bicyclic and Polycyclic Carbocations	p. 379
23.4 Vinyl Cations	p. 382
23.5 [pi]-Stabilized Carbocations	p. 384
23.6 Heteroatom Stabilized Carbocations	p. 388
23.7 Conclusions	p. 391
24 Aromaticity Indices from Magnetic Shieldings	p. 395
24.1 Introduction	p. 395
24.2 An Overview of Aromaticity Indices Based on Magnetic Shielding	p. 395
24.3 Applications	p. 401
24.4 Outlook	p. 405
25 Fullerenes	p. 409
25.1 Introduction	p. 409
25.2 Efficient Computation of NMR Parameters of Fullerenes and Their Derivatives	p. 410
25.3 Classical IPR Fullerenes	p. 411
25.4 [superscript 13]C NMR Spectra of Isomeric Fullerene Addition Compounds	p. 413
25.5 Endohedral Fullerenes	p. 414
25.6 Fullerene Dimers and Dimer-like Compounds	p. 416
25.7 Solid State NMR of Fullerenes	p. 418
25.8 Summary and Perspectives	p. 418
26 NMR of Transition Metal Compounds	p. 421
26.1 Introduction	p. 421
26.2 Ligand Chemical Shifts	p. 422
26.3 Metal Chemical Shifts	p. 424
26.4 Spin-Spin Coupling Constants	p. 427
26.5 Miscellaneous	p. 428
26.6 Conclusion and Outlook	p. 429
27 Characterization of NMR Tensors via Experiment and Theory	p. 433
27.1 Introduction	p. 433
27.2 Magnetic Shielding and Chemical Shifts	p. 434
27.3 Nuclear Spin-Spin Coupling	p. 439
27.4 NMR Spectra of Quadrupolar Nuclei in Solids	p. 443
27.5 Conclusions	p. 444
28 Calculations of Nuclear Magnetic Resonance Parameters in Zeolites	p. 449
28.1 Introduction	p. 449
28.2 Theoretical Methods	p. 451
28.3 NMR of Framework Elements: Structure Characterization	p. 453
28.4 [superscript 1]H NMR: Acidity and Proton Transfer	p. 455
28.5 NMR Studies of Guest Molecules in Zeolites: in situ NMR	p. 457
28.6 Conclusions	p. 459
Part D EPR Parameters, Methodological Aspects
29 DFT Calculations of EPR Hyperfine Coupling Tensors	p. 463
29.1 Introduction	p. 463
29.2 Theoretical Background	p. 464
29.3 The Performance of the Model	p. 467
29.4 Concluding Remarks	p. 479
30 Ab Initio Post-Hartree-Fock Calculations of Hyperfine Coupling Tensors and Their Comparison with DFT Approaches	p. 483
30.1 Introduction	p. 483
30.2 Problems Appearing in MR-CI Computations of A[subscript iso]	p. 485
30.3 Error Cancellations in Computations of A[subscript iso] with DFT	p. 489
30.4 Concluding Remarks	p. 491
31 Alternative Fermi Contact Operators for EPR and NMR	p. 493
31.1 Introduction	p. 493
31.2 Derivation of New Alternative Operators	p. 494
31.3 Formal Properties of Short-Range Alternative Operators	p. 496
31.4 EPR Calculations	p. 499
31.5 NMR Calculations	p. 501
31.6 Conclusions	p. 503
32 Calculation of EPR g-Tensors with Density Functional Theory	p. 505
32.1 Introduction	p. 505
32.2 The Physical Origin of the g-Tensor	p. 506
32.3 DFT Expressions for g-Tensors of Isolated Molecules	p. 508
32.4 Numerical Performance of the DFT Approaches	p. 519
32.5 Summary and Outlook	p. 530
33 Ab Initio Calculations of g-Tensors	p. 533
34 Zero-Field Splitting	p. 541
34.1 Introduction	p. 541
34.2 Zero-Field Splittings in EPR Spectroscopy	p. 542
34.3 Theory of Zero-Field Splittings	p. 552
34.4 Calculation of Zero-Field Splittings	p. 557
34.5 Conclusions	p. 561
Part E EPR Parameters, Applications
35 Computation of Hyperfine Coupling Tensors to Complement EPR Experiments	p. 567
35.1 Introduction	p. 567
35.2 Insight Gained from a Conventional Ab Initio Approach	p. 568
35.3 Benchmark Results Using Conventional Methods on Static Gas-phase Structures	p. 568
35.4 The Performance of Contracted Pople Basis Sets for Small Radicals Consisting Only of First-Row Atoms	p. 570
35.5 Density Functional Theory: An Alternative to a Conventional Ab Initio Approach	p. 571
35.6 Consideration of Environmental Effects	p. 572
35.7 Illustration of the Applications of DFT Methods to Biological Radicals	p. 574
35.8 Summary	p. 578
36 Applications to EPR in Bioinorganic Chemistry	p. 581
36.1 Introduction	p. 581
36.2 Biological Metal Sites	p. 582
36.3 Concluding Remark	p. 589
Index	p. 593

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