Physical methods for chemists:
Gespeichert in:
| 1. Verfasser: | |
|---|---|
| Format: | Buch |
| Sprache: | English |
| Veröffentlicht: |
Ft. Worth u.a.
Saunders College Publ. u.a.
1992
|
| Ausgabe: | 2. ed. |
| Schlagworte: | |
| Online-Zugang: | Inhaltsverzeichnis |
| Beschreibung: | 1. Aufl. u.d.T.: Drago, Russell S.: Physical methods in chemistry |
| Beschreibung: | XVII, 750 S. graph. Darst. |
| ISBN: | 0030751764 |
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Datensatz im Suchindex
| _version_ | 1804122758899040256 |
|---|---|
| adam_text | Physical
Methods for
Chemists
SECONDEDITION
RUSSELL S DRAGO
University of Florida, Gainesville
Saunders College Publishing
Harcourt Brace Jovanovich College Publishers
Ft Worth Philadelphia San Diego New York Orlando Austin
San Antonio Toronto Montreal London Sydney Tokyo
Contents
Symmetry and the Point Groups
Introduction
1-1 Definition of Symmetry
1-2 Symmetry Elements
1-3 Point Groups
1-4 Space Symmetry
1—5 Some Definitions and Applications of Symmetry
Considerations
References Cited
Additional Reading
Exercises
Group Theory and the Character Tables
2-1 Introduction
2-2 Rules for Elements that Constitute a Group
2-3 Group Multiplication Tables
2-4 Summary of the Properties of Vectors and Matrices
2-5 Representations; Geometric Transformations
2-6 Irreducible Representations
* 2-7 Character Tables
2-8 Non-Diagonal Representations
2-9 More on Character Tables
2-10 More on Representations
2-11 Simplified Procedures for Generating and Factoring Total
Representations: The Decomposition Formula
2-12 Direct Products
Additional Reading
Exercises
Molecular Orbital Theory and Its Symmetry Aspects
Introduction
3-1 Operators
3-2 A Matrix Formulation of Molecular Orbital Calculations
3-3 Perturbation Theory
Symmetry in Quantum Mechanics
3-4 Wave Functions as a Basis for Irreducible Representations
3-5 Projecting Molecular Orbitals
Molecular Orbital Calculations
3-6 Hiickel Procedure
3-7 Properties Derived from Wave Functions
3-8 Extended Hiickel Procedure
3-9 SCF-INDO (Intermediate Neglect of Differential Overlap)
3-10 Some Predictions from M O Theory on Alternately Double
Bonded Hydrocarbons
3-11 More on Product Ground State Wave Functions
References Cited
Additional Reading
Compilations
Exercises
General Introduction to Spectroscopy
4-1 Nature of Radiation
4-2 Energies Corresponding to Various Kinds of Radiation
4-3 Atomic and Molecular Transitions
4-4 Selection Rules
4=5 Relaxation and Chemical Exchange Influences on Spectral
Line-Width
General Applications
4-6 Determination of Concentration
4-7 Isosbestic Points
4-8 Job s Method of Isomolar Solutions
4-9 Fingerprinting
References Cited
Exercises
Electronic Absorption Spectroscopy
Introduction
5-1 Vibrational and Electronic Energy Levels in a Diatomic
Molecule 109
Contents
5-2 Relationship of Potential Energy Curves to Electronic Spectra 111
5-3 Nomenclature 113
Assignment of Transitions 117
5-4 Spin-Orbit Coupling 117
5-5 Configuration Interaction 117
5-6 Criteria to Aid in Band Assignment 118
The Intensity of Electronic Transitions 120
5-7 Oscillator Strengths 120
5-8 Transition Moment Integral 120
5-9 Derivation of Some Selection Rules 123
5-10 Spectrum of Formaldehyde 123
5-11 Spin-Orbit and Vibronic Coupling Contributions to Intensity 124
5-12 Mixing of d and p Orbitals in Certain Symmetries 126
5-13 Magnetic Dipole and Electric Quadrupole Contributions to
Intensity 127
5-14 Charge Transfer Transitions 127
5-15 Polarized Absorption Spectra 128
Applications 130
5-16 Fingerprinting 130
5-17 Molecular Addition Compounds of Iodine 133
5-18 Effect of Solvent Polarity on Charge-Transfer Spectra 135
5-19 Structures of Excited States 137
Optical Rotary Dispersion, Circular Dichroism, and
Magnetocircular Dichroism 137
5-20 Introduction 137
5-21 Selection Rules 139
5-22 Applications 140
5-23 Magnetocircular Dichroism 141
References__Cited 143
Additional References _ 144
Exercises 145
Vibration and Rotation Spectroscopy: Infrared, Raman, and Microwave 149
Introduction 149
6-1 Harmonic and Anharmonic Vibrations 149
6-2 Absorption of Radiation by Molecular Vibrations—
Selection Rules 150
6-3 Force Constant 151
Vibrations in a Polyatomic Molecule 153
6-4 The 3AT - 6(5) Rule
6-5 Effects Giving Rise to Absorption Bands
6-6 Normal Coordinate Analyses and Band Assignments 156
6-7 Group Vibrations and the Limitations of This Idea 160
Raman Spectroscopy 162
6-8 Introduction 162
6-9 Raman Selection Rules 164
6-10 Polarized and Depolarized Raman Lines 168
6-11 Resonance Raman Spectroscopy 170
Symmetry Aspects of Molecular Vibrations 172
6-12 Significance of the Nomenclature Used to Describe Various
Vibrations 172
6-13 Use of Symmetry Considerations to Determine the Number
of Active Infrared and Raman Lines 172
6-14 Symmetry Requirements for Coupling, Combination Bands,
and Fermi Resonance 176
6-15 Microwave Spectroscopy 177
6-16 Rotational Raman Spectra 179
Applications of Infrared and Raman Spectroscopy 179
6-17 Procedures 179
6-18 Fingerprinting 184
6-19 Spectra of Gases 186
6-20 Application of Raman and Infrared Selection Rules to the
Determination of Inorganic Structures 192
Bond Strength-Frequency Shift Relations 194
6-21 Changes in the Spectra of Donor Molecules upon
Coordination 196
6-22 Change in Spectra Accompanying Change in Symmetry
upon Coordination 198
References Cited 202
Additional References 205
Exercises -- 206
Nuclear Magnetic Resonance Spectroscopy—Elementary Aspects 211
Introduction 211
Classical Description of the NMR Experiment—The Bloch
Equations 212
7-1 Some Definitions 212
7-2 Behavior of a Bar Magnet in a Magnetic Field 213
7-3 Rotating Axis Systems 214
7-4 Magnetization Vectors and Relaxation 215
7-5 The NMR Transition 217
7-6 The Bloch Equations 218
7-7 The NMR Experiment 220
Contents
The Quantum Mechanical Description of the NMR Experiment 224
7-8 Properties of J 224
7-9 Transition Probabilities 225
Relaxation Effects and Mechanisms 227
7-10 Measuring the Chemical Shift 229
7-11 Interpretation of the Chemical Shift 232
7-12 Interatomic Ring Currents 241
7-13 Examples of Chemical Shift Interpretation 241
Spin-Spin Splitting 243
7-14 Effect of Spin-Spin Splitting on the Spectrum 243
7-15 Discovering Non-Equivalent Protons 246
7-16 Effect of the Number and Nature of the Bonds on
Spin-Spin Coupling 247
7-17 Scalar Spin-Spin Coupling Mechanisms 249
7-18 Application of Spin-Spin Coupling to Structure
Determination 252
Factors Influencing the Appearance of the NMR Spectrum 257
7-19 Effect of Fast Chemical Reactions on the Spectrum 257
7-20 Quantum Mechanical Description of Coupling 259
7-21 Effects of the Relative Magnitudes of J and A on the Spectrum
of an AB Molecule 263
7-22 More Complicated Second-Order Systems 265
7-23 Double Resonance and Spin-Tickling Experiments 267
7-24 Determining Signs of Coupling Constants 268
7-25 Effects on the Spectrum of Nuclei with Quadrupole Moments 269
References Cited 271
Compilations of Chemical Shifts 272
Exercises 273
Dynamic and Fourier Transform NMR 290
Introduction 290
Evaluation of Theormodynamic Data with NMR 290
NMR Kinetics 291
8-1 Rate Constants and Activation Enthalpies from NMR 291
8-2 Determination of Reaction Orders by NMR 295
8-3 Some Applications of NMR Kinetic Studies 297
8-4 Intramolecular Rearrangements Studied by NMR—
Fluxional Behavior 300
8-5 Spin Saturation Labeling 305
8-6 The Nuclear Overhauser Effect 306
Fourier Transform NMR 309
8-7 Principles 309
8-8 Optimizing the FTNMR Experiment 314
8-9 The Measurement of T, by FTNMR 315
8-10 Use of Tj for Peak Assignments 317
8-11 NMR of Quadrupolar Nuclei 319
Applications and Strategies in FTNMR 319
8-12 13C 319
8-13 Other Nuclei 323
More on Relaxation Processes 326
8-14 Spectral Density 326
Multipulse Methods 328
8-15 Introduction 328
8-16 Spin Echoes 329
8-17 Sensitivity-Enhancement Methods 331
8-18 Selective Excitation and Suppression 332
8-19 Two-Dimensional NMR 334
NMR in Sol ids and Liquid Crystals 340
8-20 Direct Dipolar Coupling 340
8-21 NMR Studies of Solids 341
8-22 NMR Studies in Liquid Crystal Solvents 342
8-23 High Resolution NMR of Solids 347
References Cited 348
Additional References 351
Exercises 352
Electron-Paramagnetic Resonance Spectroscopy 360
Introduction 360
9-1 Principles 360
Nuclear Hyperfine Splitting 363
9-2 The Hydrogen Atom 363
9-3 Presentation of the Spectrum 368
9-4 Hyperfine Splittings in Isotropic Systems Involving More
Than One Nucleus 370
9-5 Contributions to the Hyperfine Coupling Constant in
Isotropic Systems 374
Anisotropic Effects 380
9-6 Anisotropy in the g Value 380
9-7 Anisotropy in the Hyperfine Coupling 383
9-8 The EPR of Triplet States 390
Contents
9-9 Nuclear Quadrupole Interaction 392
9-10 Line Widths in EPR 394
9-11 The Spin Hamiltonian 396
9-12 Miscellaneous Applications 397
References Cited 400
Additional References 401
Exercises 401
The Electronic Structure and Spectra of Transition Metal Ions 409
Introduction 409
Free Ion Electronic States 409
10-1 Electron-Electron Interactions and Term Symbols 409
10-2 Spin-Orbit Coupling in Free Ions 413
Crystal Fields 416
10-3 Effects of Ligands on the d Orbital Energies 416
10-4 Symmetry Aspects of the d Orbital Splitting by Ligands 419
10-5 Double Groups 427
10-6 The Jahn-Teller- Effect 429
10-7 Magnetic Coupling in Metal Ion Clusters 430
Applications 433
10-8 Survey of the Electronic Spectra of Oh Complexes 433
10-9 Calculation of Dq and /? for Oh Ni(II) Complexes 437
10-10 Effect of Distortions on the d Orbital Energy Levels 443
10-11 Structural Evidence from the Electronic Spectrum 447
Bonding Parameters from Spectra 450
10-12 a and n Bonding Parameters from the Spectra of
Tetragonal Complexes 450
10-13 The Angular Overlap Model 452
Miscellaneous Topics Involving Electronic Ttransitions 458
10-14 Electronic Spectra of Oxo-Bridged Dinuclear Iron Centers 458
10-15 Intervalence Electron Transfer Bands 459
10-16 Photoreactions 462
References Cited 462
Exercises 463
Magnetism 469
11-1 Introduction
11-2 Types of Magnetic Behavior
Contents
11-3 Van Vleck s Equation 476
11-4 Applications of Susceptibility Measurements 483
11—5 Intramolecular Effects 486
11-6 High Spin-Low Spin Equilibria 489
11-7 Measurement of Magnetic Susceptibilities 490
11-8 Superparamagnetism 491
References Cited 494
Exercises 496
Nuclear Magnetic Resonance of Paramagnetic Substances in Solution 500
by Ivano Bertini and C Luchinat
12-1 Introduction 500
12-2 Properties of Paramagnetic Compounds 501
12-3 Considerations Concerning Electron Spin 503
12-4 The Contact Shift 507
12-5 The Pseudocontact Shift 508
12-6 Lanthanides 510
12-7 Factoring the Contact and Pseudocontact Shifts 512
12-8 The Contact Shift and Spin Density 514
12-9 Factors Affecting Nuclear Relaxation in Paramagnetic
System 519
12-10 Relaxometry 524
12-11 Electronic Relaxation Times 527
12-12 Contrast Agents 530
12-13 Trends in the Development of Paramagnetic NMR 531
12-14 Some Applications 534
12-15 The Investigation of Bimetallic Systems 543
References Cited 552
Exercises 556
Electron Paramagnetic Resonance Spectra of Transition Metal Ion
Complexes 559
13-1 Introduction 559
13-2 Interpretation of the g-Values 564
13-3 Hyperfine Couplings and Zero Field Splittings 571
13-4 Ligand Hyperfine Couplings 576
13-5 Survey of the EPR Spectra of First-Row Transition Metal Ion
Complexes 578
13-6 The EPR of Metal Clusters 591
1J-7 Double Resonance and Fourier Transform EPR Techniques 594
References Cited
Additional References
Exercises
Contents
Nuclear Quadrupole Resonance Spectroscopy, NQR 604
14-1 Introduction 604
14-2 Energies of the Quadrupole Transitions 607
14-3 Effect of a Magnetic Field on the Spectra 611
14-4 Relationship Between Electric Field Gradient and
Molecular Structure 612
14-5 Applications 616
14-6 Double Resonance Techniques 620
References Cited 622
Additional References 623
Exercises 624
Mossbauer Spectroscopy 626
15-1 Introduction 626
15-2 Interpretation of Isomer Shifts 630
15-3 Quadrupole Interactions 631
15-4 Paramagnetic Mdssbauer Spectra 633
15-5 Mossbauer Emission Spectroscopy 635
15-6 Applications • 635
References Cited 646
Series 646
Exercises 647
Ionization Methods: Mass Spectrometry, Ion Cyclotron Resonance,
Photoelectron Spectroscopy 650
Mass Spectrometry 650
16-1 Instrument Operation and Presentation of Spectra 650
16-2 Processes That Can Occur When a Molecule and a High
Energy Electron Combine 655
16-3 Fingerprint Application 657
16-4 Interpretation of Mass Spectra 659
16-5 Effect of Isotopes on the Appearance of a Mass
Spectrum 660
16-6 Molecular Weight Determinations; Field Ionization
Techniques 662
16-7 Evaluation of Heats of Sublimation and Species in the
Vapor Over High Melting Solids 663
16-8 Appearance Potentials and Ionization Potentials 664
FTICR/MS 665
16-9 The Fourier Transform Ion Cyclotron Resonance Technique 665
Surface Science Techniques 667
16-10 Introduction 667
16-11 Photoelectron Spectroscopy 667
16-12 SIMS (Secondary Ion Mass Spectrometry) 677
16-13 LEED, AES, and HREELS Spectroscopy 678
16-14 STM (Scanning Tunneling Microscopy) and AFM
(Atomic Force Microscopy) 680
EXAFS and XANES 681
16-15 Introduction 681
16-16 Applications 682
References Cited 682
Exercises 685
X-Ray Crystallography 689
by Joseph W Ziller and Arnold L Rheingold
17-1 Introduction 689
Principles 690
17-2 Diffraction of X-Rays 690
17-3 Reflection and Reciprocal Space 691
17-4 The Diffraction Pattern 693
17-5 X-Ray Scattering by Atoms and Structures 693
Crystals 695
17-6 Crystal Growth 695
17-7 Selection of Crystals 696
17-8 Mounting Crystals 697
Methodology 698
f7-9 Diffraction Equipment 698
17-10 Diffractometer Data Collection 699
17-11 Computers 700
Some Future Developments 700
17-12 Area Detectors 700
17-13 X-Ray versus Neutron Diffraction 701
17-14 Synchrotron Radiation 701
Symmetry and Related Concerns 701
17-15 Crystal Classes 701
17-16 Space Groups 703
17-17 Space-Group Determination 704
17-18 Avoiding Crystallographic Mistakes 705
17-19 Molecular versus Crystallographic Symmetry 707
17-20 Quality Assessment 707
17-21 Crystallographic Data 710
Contents
References Cited 711
Exercises 711
Appendix A
Character Tables for Chemically Important Symmetry Groups 713
Appendix B
Character Tables for Some Double Groups 724
Appendix C
Normal Vibration Modes for Common Structures 727
Appendix D
Tanabe and Sugano Diagrams for Oh Fields 732
Appendix E
Calculation of A (10Dq) and 0 for 0„ Ni and Td Co Complexes 735
Appendix F
Conversion of Chemical Shift Data 739
Appendix G
Solution of the Secular Determinant for the NMR Coupling of the AB Spin
System 740
Index 745
|
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| genre | (DE-588)4123623-3 Lehrbuch gnd-content |
| genre_facet | Lehrbuch |
| id | DE-604.BV008380974 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T17:18:58Z |
| institution | BVB |
| isbn | 0030751764 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-005526585 |
| oclc_num | 24796496 |
| open_access_boolean | |
| owner | DE-355 DE-BY-UBR |
| owner_facet | DE-355 DE-BY-UBR |
| physical | XVII, 750 S. graph. Darst. |
| publishDate | 1992 |
| publishDateSearch | 1992 |
| publishDateSort | 1992 |
| publisher | Saunders College Publ. u.a. |
| record_format | marc |
| spelling | Drago, Russell S. Verfasser aut Physical methods for chemists Russell S. Drago 2. ed. Ft. Worth u.a. Saunders College Publ. u.a. 1992 XVII, 750 S. graph. Darst. txt rdacontent n rdamedia nc rdacarrier 1. Aufl. u.d.T.: Drago, Russell S.: Physical methods in chemistry Analyse spectrale ram Chimie physique et théorique ram Spectroscopie ram Chemistry, Physical and theoretical Spectrum analysis Chemie (DE-588)4009816-3 gnd rswk-swf Spektroskopie (DE-588)4056138-0 gnd rswk-swf Physikalisches Verfahren (DE-588)4315730-0 gnd rswk-swf Spektralanalyse (DE-588)4132368-3 gnd rswk-swf Theoretische Chemie (DE-588)4185098-1 gnd rswk-swf (DE-588)4123623-3 Lehrbuch gnd-content Theoretische Chemie (DE-588)4185098-1 s DE-604 Chemie (DE-588)4009816-3 s Physikalisches Verfahren (DE-588)4315730-0 s Spektroskopie (DE-588)4056138-0 s 1\p DE-604 Spektralanalyse (DE-588)4132368-3 s 2\p DE-604 HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=005526585&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis 1\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk 2\p cgwrk 20201028 DE-101 https://d-nb.info/provenance/plan#cgwrk |
| spellingShingle | Drago, Russell S. Physical methods for chemists Analyse spectrale ram Chimie physique et théorique ram Spectroscopie ram Chemistry, Physical and theoretical Spectrum analysis Chemie (DE-588)4009816-3 gnd Spektroskopie (DE-588)4056138-0 gnd Physikalisches Verfahren (DE-588)4315730-0 gnd Spektralanalyse (DE-588)4132368-3 gnd Theoretische Chemie (DE-588)4185098-1 gnd |
| subject_GND | (DE-588)4009816-3 (DE-588)4056138-0 (DE-588)4315730-0 (DE-588)4132368-3 (DE-588)4185098-1 (DE-588)4123623-3 |
| title | Physical methods for chemists |
| title_auth | Physical methods for chemists |
| title_exact_search | Physical methods for chemists |
| title_full | Physical methods for chemists Russell S. Drago |
| title_fullStr | Physical methods for chemists Russell S. Drago |
| title_full_unstemmed | Physical methods for chemists Russell S. Drago |
| title_short | Physical methods for chemists |
| title_sort | physical methods for chemists |
| topic | Analyse spectrale ram Chimie physique et théorique ram Spectroscopie ram Chemistry, Physical and theoretical Spectrum analysis Chemie (DE-588)4009816-3 gnd Spektroskopie (DE-588)4056138-0 gnd Physikalisches Verfahren (DE-588)4315730-0 gnd Spektralanalyse (DE-588)4132368-3 gnd Theoretische Chemie (DE-588)4185098-1 gnd |
| topic_facet | Analyse spectrale Chimie physique et théorique Spectroscopie Chemistry, Physical and theoretical Spectrum analysis Chemie Spektroskopie Physikalisches Verfahren Spektralanalyse Theoretische Chemie Lehrbuch |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=005526585&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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