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The Physical Chemist’s Toolbox
The Physical Chemist’s Toolbox
Second Edition
Robert M. Metzger
Department of Chemistry and Biochemistry
The University of Alabama
Tuscaloosa and Birmingham, Alabama, USA
This second edition first published 2023
© 2023 John Wiley & Sons, Inc.
Edition History
John Wiley & Sons (1e, 2012)
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v
Contents
Foreword xvii
Preface and Philosophy xix
About the Companion Website xxiii
1 Fundamental Particles, Fundamental Forces, and Mathematical Tools 1

1.0 Introduction 1
1.1 Fundamental Forces, Elementary Particles, Nuclei, and Atoms 2
1.2 Force One: Gravitation 16
1.3 Force Three: Weak Force 17
1.4 Force Four: Strong Force 17
1.5 Review of Mathematical Concepts 24
1.5.1 Mathematics and Statistics 24
1.5.2 Functions, Equations, and Functionals 24
1.5.3 Quadratic, Cubic, and Quartic Equations 24
1.5.4 Partial Derivatives 27
1.5.5 Jacobians 30
1.5.6 Line integral 30
1.5.7 The Gauss–Green–Stokes Theorem 30
1.5.8 Techniques of integration 31
1.5.9 Differential Forms 33
1.5.10 Infinite Series 33
1.5.11 Sum and Integral Killers: The Kronecker Delta and the Dirac Delta Function 34
1.5.12 Ordinary Differential Equations (ODEs) 35
1.5.13 The Lagrange Method of Undetermined Multipliers 37
1.5.14 Partial Differential Equations (PDEs) 38
1.6 Mechanics, Vectors, Tensors, and Determinants 39
1.6.1 Forces and Linear Momentum 39
1.6.2 Dimensional Analysis 39
1.6.3 Unit Systems 39
1.6.4 Vectors 41
1.6.5 Determinants 42
1.6.6 Matrices 44
1.6.7 Tensors 45
1.6.8 Similarity Transformations 45
1.6.9 Eigenvalue-Eigenvector Problem 46
1.6.10 Planar Rotations 47
1.6.11 Eulerian Rotations 48
1.6.12 Covariant and Contravariant Vectors and Tensors 49
1.6.13 Covariant 49
1.6.14 Moment of Inertia and Angular Momentum 50
1.6.15 Derivative Operators: “Ski Slopes,” “Hernias,” and “Curls” 51
1.6.16 Gradient 52
vi Contents
1.6.17 Divergence 52
1.6.18 Curl 52
1.6.19 Gauss–Green–Stokes Theorem 53
1.6.20 Combinatorics 54
1.7 Hooke’s Law, One-dimensional Chain, Dispersion Relations, and Stress–Strain Tensors 55
1.7.1 Longitudinal Mechanical Waves Subjected to Hooke’s Law 57
1.7.2 Longitudinal Elastic Waves in a 1D Array of Equal Masses and Springs 57
1.7.3 One-dimensional Chain with Two Kinds of Atoms: A Band Gap Appears 59
1.7.4 Stress and Strain Tensors 61
1.8 Lagrange’s Function and Hamilton’s Function 62
1.9 Force Two: Electromagnetism 63
1.9.1 Coulomb’s Law and Ampère’s Law 63
1.9.2 Material Media and Their Reaction to External Fields 65
1.9.3 Maxwell’s Equations 66
1.9.4 Scalar and Vector Potentials 70
1.9.5 Polarization of Electromagnetic Waves 71
1.9.6 Multipoles 72
1.9.7 Electric Dipole Moments 73
1.9.8 Electric Multipole Moments, Polarizabilities and Hyperpolarizabilities 73
1.10 The Size of Fundamental Particles and the Physical Meaning of Quantum Numbers 74
1.11 Special Relativity 75
1.12 Feynman Diagrams 79
1.13 General Relativity, Gravity as a Curvature of Space-Time and the Size of the Universe 80
1.14 Elements of Optics 83
1.14.1 Jones Vector 88
1.14.2 Anisotropic Indices of Refraction 88
1.14.3 Mirrors 89
1.14.4 Prisms and Gratings 92
1.15 Transforms 94
1.15.1 Convolution Theorem 97
1.15.2 Laplace Transforms 98
1.15.3 Wavelet Transform 100
1.16 Contour Integration and Kramers–Kronig Relations 100
1.17 Error Analysis 102
1.17.1 Errors 102
1.17.2 Propagation of Errors 102
1.17.3 Gaussian Normal Error Probability Function 103
1.17.4 Binomial Distribution 104
1.17.5 Poisson Distribution 104
1.17.6 Least Squares or Linear Regression Analysis 104
1.18 Statistics 105
1.19 General References 107
References 137
End-of-Chapter Problems 138
2 Quantum Mechanics 147

2.0 Introduction 147
2.1 Quantum Postulates 147
2.1.1 Bras, Kets, and Hermitian Operators 151
2.2 Quantum Mechanics of the Free Electron 154
2.3 The Particle in a Box 155
2.3.1 Tunneling or Barrier Penetration or Scattering in One Dimension 157
2.3.2 Radioactive Decay 160
Contents vii
2.3.3 Gamow Calculation 161

2.4 The Harmonic Oscillator 162
2.5 The Hamiltonian for the One-electron Atom in a Central Field 165
2.6 The Rigid Rotor 173
2.7 The Hamiltonian and Eigenfunctions for the N-electron Atom or Molecule 174
2.8 Space Quantization: the Allowed Orientations of Orbital and Spin Angular Momenta 175
2.9 Aufbau for Atoms 176
2.10 Lewis Octets 177
2.11 Promotion and Hybridization of Atomic Orbitals 177
2.12 Bonding in Hydrogen Molecule: Valence Bond vs. Molecular Orbital and Variational Approaches 178
2.13 Aufbau for Molecules: σ and π Bonding 179
2.14 Perturbation Theory 182
2.15 The Hartree–Fock Method 184
2.16 The Roothaan–Hall Matrix Formulation of the Hartree–Fock Problem 185
2.17 Implementation of the Hartree–Fock Method 189
2.18 Configuration Interaction 190
2.19 Density Functional Theory (DFT) 191
2.20 Molecular Mechanics 194
2.21 The Hückel Problem, or “Simple” Hückel Molecular Orbital Theory (SHMO) 194
2.22 Extended Hückel Theory 199
2.23 Pariser–Parr–Pople Theory 199
2.24 Neglect of Differential Overlap (NDO) Methods 200
2.25 Magnetic Moments, Landé g-factor, Larmor Precession, Spin–Orbit Coupling, and Thomas Precession 204
2.25.1 Larmor Precession 206
2.25.2 The g = 2 Puzzle, Stated 208
2.25.3 Spin–Orbit Interaction 208
2.25.4 The g = 2 Puzzle Solved: Thomas Precession 209
2.26 More Terms of the Hamiltonian Operator for a Many-Electron Atom or Molecule 211
2.27 “Van der Waals” Interactions in Molecules 214
2.28 Atomic Structure: LS (Russell–Saunders) vs. jj Coupling 216
2.29 Molecular Spectroscopy 219
2.30 Einstein A and B Coefficients 223
2.31 Absorption of Light: Beer–Bouguer–Lambert Law, or Beer’s Law 225
2.32 Time-Dependent Perturbation Theory: The Rabi Formula 227
2.33 Fermi’s Golden Rule 229
2.34 Photon–Molecule Interaction – The Hamiltonian 232
2.35 Transition Moments and Einstein Coefficients 235
2.35.1 Oscillator Strength 236
2.36 Quantum Electrodynamics 236
2.37 General Radiative Transitions 237
2.38 Static vs. Resonant Detection 239
2.39 Static Electric–Dipole Selection Rules for the One-Electron Atom 239
2.40 Static Electric-Dipole Selection Rules for the Harmonic Oscillator 240
2.41 Lifetimes from Resonance Lineshapes 241
2.42 Light Scattering 241
References 271
3 Thermodynamics 277
3.0 Review of Thermodynamics 277
3.1 The Three (Plus One) Laws of Thermodynamics 277
3.1.1 Zeroth Law of Thermodynamics (Transitivity) 277
3.1.2 First Law of Thermodynamics (Conservation of Energy – “You Can’t Win”) 277
viii Contents
3.1.3 Second Law of Thermodynamics (“You Cannot Even Break Even”) 278
3.1.4 Third Law of Thermodynamics 278
3.2 Useful Auxiliary Functions: Enthalpy, Helmholtz Free Energy, and Gibbs Free Energy 279
3.3 Perfect Differentials (Two-Forms) 279
3.4 Useful Measurables: Thermal Expansivity, Heat Capacity, Joule–Thomson and Isothermal Thompson
Coefficients, and the Chemical Potential 281
3.5 Gibbs Phase Rule 283
3.6 Crystalline and Amorphous Solids 284
3.7 Liquids 284
3.8 Perfect Gas Law, the PVT Surface, the van der Waals Equation and Virial Equations 285
3.9 Arrhenius Assumption 290
3.10 More About Gases: Maxwell–Boltzmann Distribution, Collision Frequency, Mean Free Path, and Gaseous
Effusion 291
3.11 More About Liquids 292
3.11.1 Osmosis 293
3.11.2 Superfluid 294
3.12 More About Solids 294
3.12.1 Magnetic Solids 294
3.12.2 Electrets 295
3.13 Liquid Crystals 295
3.14 Two-component Liquid–Vapor Phase Diagrams 295
3.15 Two-component Solid–Liquid Phase Diagrams for Solid–Liquid Equilibria 298
3.16 The Chemical Potential, Ideal Solutions, and Colligative Properties 298
3.16.1 Freezing-Temperature Depression 299
3.17 Two-Dimensional Version of the Perfect Gas Law 300
3.17.1 Micelles and Liposomes 304
3.18 Contact Angle and Surface Tension Measurements 306
3.19 Adiabatic and Diathermal Walls and Fixed-Temperature Baths 308
3.20 Thermodynamic Efficiency: The Carnot, Otto, Diesel, and Rankine Cycles 308
3.21 International Standards for Time, Mass, Length, Temperature, and Brightness 310
3.22 Standard States and Enthalpies and Gibbs Free Energies of Formation 311
3.23 Bond Enthalpies 313
3.24 Electronegativity 318
3.25 Reaching for High and Low Temperatures 320
3.26 Attainment of High and Low Pressures 321
References 321
4 Statistical Mechanics 327

4.1 Replicas and Ensembles, Fermions, Bosons, and Boltzons 328
4.1.1 Fermion Postulate 329
4.1.2 Boson Postulate 329
4.1.3 Boltzon Postulate 329
4.2 CB, FD, and BE Distributions, and the Microcanonical Ensemble 330
4.2.1 Maximum Probability 331
4.3 Canonical, Grand Canonical, Isothermal-Isobaric, and Generalized Ensembles 333
4.4 Links Between the Partition Functions and Some Thermodynamic Functions 338
4.5 Heat Capacities 338
4.5.1 Translation 339
4.5.2 Rotation 339
4.5.3 Nuclear Spin Effects on Rotation 340
4.5.4 Vibration 341
Contents ix
4.5.5 Electronic Excitation 341

4.5.6 Einstein and Debye Theories of the Low-temperature Heat Capacity of Solids [4.2] 342
4.5.7 Debye Theory of the Heat Capacity of Solids 342
4.6 Black-Box Radiation, and the Birth of Quantum Mechanics 343
4.7 Electronic Heat Capacity: Drude vs. Fermi–Dirac 346
4.8 Magnetic Susceptibilities 349
4.8.1 General Phenomenology 349
4.8.2 Dilute Ensemble of Paramagnetic Ions 350
4.8.3 Diamagnetism 352
4.8.4 Ferromagnetism 355
4.9 Electric Susceptibilities 356
4.10 Universal Theory of Critical Phenomena 360
References 360
5 Kinetics, Equilibria, and Electrochemistry 363

5.1 Energetics, Reaction Coordinate, Transition States, Intermediates, and Catalysis 363
5.2 Classification of Reaction Types 367
5.3 First-Order and Unimolecular Reactions 368
5.3.1 Carbon-14 Dating 368
5.4 Second-Order (Unmixed) and Unmixed Bimolecular Reactions 369
5.5 Second-Order (Mixed) and Mixed Bimolecular Reactions 369
5.6 Third-Order (Unmixed) and Unmixed Termolecular Reactions 370
5.7 Reversible Reactions 370
5.8 Consecutive Reactions 371
5.9 The Steady-State Approximation and the Rate-Determining Step 372
5.10 Approximation Methods: the Michaelis–Menten Equation 372
5.11 Chain Reactions. The Reaction of Hydrogen and Bromine at High Temperature 375
5.12 Using Laplace Transforms to Solve Kinetics Equations 377
5.13 Reaction Rate Theories and Energy Surfaces 378
5.14 Marcus Theory of Electron Transfer 380
5.15 Equilibria in Aqueous Solution: pH 383
5.16 Equilibria in Nonaqueous Solvents 391
5.17 Lewis Acids and Lewis Bases 392
5.18 Electrochemistry: Electrode Potentials and the Nernst Equation 393
5.19 Gouy–Chapman Double-Layer Theory 405
5.20 Nernst–Planck and Cottrell Equations 406
Further Reading 409
References 409
6 Symmetry 411
6.0 Symmetry 411
6.1 Symmetry in Crystals 411
6.2 Symmetry Operations and Point Groups 412
6.3 Group Theory and Character Tables 418
6.4 Bravais Lattices 427
6.5 The 32 Crystallographic Point Groups 432
6.6 The 17 Plane Groups 433
6.7 The 230 Crystallographic Space Groups 434
6.8 Listing of Elements, Simple Compounds, and Their Crystal Structures 443
6.9 The Wigner–Seitz Cell 455
x Contents
6.10 Reciprocal Lattice 456

6.11 Symmetry of 2D Surfaces 458
6.12 Descent of Symmetry 459
6.13 Covariant and Contravariant Transformations 459
6.13.1 Covariant 459
6.13.2 Contravariant 460
6.13.3 Four by Four 461
6.13.4 Generation of 230 Space Groups Using 4 by 4 Matrices 462
6.14 Example of Descent of Symmetry: VO2 462
References 466
7 Solid State Physics 469

7.1 Electrical Resistance, Hall Effect, Drude Model, Tunneling, and the Landauer Formula 469
7.2 Fermi–Dirac Statistics for Electron Gas: Sommerfeld Model 479
7.3 X-ray Diffraction 484
7.4 Quantum Numbers in a Macroscopic Solid: Bloch Waves 487
7.5 Bloch Waves in One Dimension and Dispersion Relations 488
7.6 Band Structures 490
7.7 Theoretical Methods for Computing Wavefunctions in Solids 495
7.7.1 The Tight-Binding Method 495
7.7.2 Cellular Method 497
7.7.3 Band Structure for the Muffin-tin Potential 498
7.7.4 Augmented Plane Waves (APW) 498
7.7.5 Orthogonalized Plane Waves (OPW) 498
7.7.6 Hubbard Hamiltonian 498
7.8 Mixed Valence and One-Dimensional Instabilities 498
7.9 Defects and Mobile Excitations in Solids and Molecules 500
7.10 Superconductivity 501
7.11 Lattice Energies: Madelung, Repulsion, Dispersion, Dipole–dipole, and Others 505
References 515
8 Electrical Circuits, Amplifiers, and Computers 519

8.1 Electrical Components 519
8.2 Simple Circuits with No Rectification or Amplification 521
8.2.1 Resistors 522
8.2.2 Capacitance 522
8.2.3 Capacitors 522
8.2.4 Inductance 523
8.2.5 Inductors 523
8.2.6 Kirchhoff’s Rules for Circuits 523
8.2.7 Series RLC Circuit 524
8.3 Vacuum Tube Diode 528
8.4 Vacuum Tube Triode 530
8.5 Conduction in Pure and Doped Si and Ge 533
8.6 Rectification in pn Junction Diodes or Rectifiers 536
8.7 pnp and npn Transistors 540
8.8 Small-Signal Theory for Transistors 546
8.9 Large-Signal Behavior of Junction Transistors 549
8.10 Unipolar or Field-Effect Transistors (FET) 550
8.11 JFETs 554
8.12 Operational Amplifiers 554
Contents xi
8.13 Historical Introduction to Computers 557

8.14 Elementary Digital Concepts 558
8.15 Computer Architecture 560
8.16 Compilers 561
8.17 Simple Programming 562
8.18 Communicating with a Computer Operating System Commands 562
References 574
9 Sources, Sensors, and Detection Methods 577

9.1 Cosmic Rays 577
9.2 Source: Isotopes and Fission Energy Sources 578
9.3 Source: Solar Energy 583
9.4 Source: Earth-Based Nuclear Fusion 588
9.5 Source: Photovoltaic Cells 589
9.6 X-rays 592
9.7 Cherenkov and Synchrotron Radiation, Bremsstrahlung 597
9.8 Conventional Light Sources 597
9.9 Microwave Sources 598
9.10 Masers and Lasers 599
9.11 Lightning 606
9.12 St. Elmo Fire 606
9.13 Aurora Borealis 607
9.14 Fireflies 607
9.15 Arcs and Sparks 607
9.16 Flames 607
9.17 Light-Emitting Diodes: Inorganic, Organic, and Polymeric 608
9.18 Chemical Explosives and High-Energy Compounds 609
9.19 Storage Batteries and Electrochemical Cells 610
9.19.1 Practical Cells and Batteries 613
9.20 Generation of High Voltages 615
9.21 Time Sensors 615
9.22 Mass Sensors 615
9.22.1 Two-Pan Balances 615
9.22.2 Magnetically Damped One-Pan Balances 616
9.22.3 Load-Cell Balances 616
9.22.4 Force-Coil Analytical Balances 616
9.22.5 Thermogravimetric Analyzer (TGA) 616
9.22.6 Quartz Crystal Microbalance 617
9.23 Temperature Sensors 617
9.23.1 Liquid in Glass Thermometers 617
9.23.2 Platinum Resistance Thermometer 617
9.23.3 Thermistors 618
9.23.4 Bolometers 618
9.23.5 Quartz Crystal Thermometer 620
9.23.6 Pyrometers 620
9.24 Pressure Sensors 620
9.24.1 Mercury Manometer 621
9.25 Heat Capacities 622
9.26 Photographic Plates and Films 623
9.27 Wilson Cloud Chamber and Glaser H2 Bubble Chamber 624
9.28 Scintillation Counter 624
xii Contents
9.29 Geiger–Müller Counter 624

9.30 Proportional Counters 624
9.31 Spark Chamber 624
9.32 Photomultipliers 625
9.33 X-ray Area Detectors (Array Detectors) 625
9.34 X-ray and Infrared Fluoroscopy and Image Intensifiers 625
9.35 Direct Semiconductor Detectors 625
9.36 Charge-Coupled Devices 626
9.37 Photoelectric Cells 626
9.38 Interferometers 627
9.39 Superconducting Quantum Interference Device Magnetometers 628
9.40 Absorption Wavemeter 630
9.41 Magnetometers 630
9.42 Voltage Sensors 631
9.43 Slits and Bandwidth 632
9.44 Noise 632
9.45 Phase-Sensitive Detection or Lock-in Amplifiers 633
9.46 Heterodyne Detection 633
9.47 Derivative Detection 634
References 634
10 Instruments 635
10.1 Physical Separations: Fractional Crystallization and Distillation 635
10.2 Chromatography 637
10.3 Biochemical Synthesizers and Polymerase Chain Reaction 639
10.4 Elemental Analysis 639
10.5 Mass Spectrometry 640
10.5.1 Application (Developed by C. Cassady): Analysis of Peptides by MALDI/TOF-MS 643
10.5.2 Application: Ionization and Electron Affinity 646
10.5.3 Combination Instruments 648
10.6 Optical and Electron Microscopy 649
10.7 Scanned Probe Microscopies: STM, AFM, MFM, and LFM 651
10.8 X-ray Diffraction of Ordered Crystals, Liquids, and Disordered Solids 656
10.8.1 X-ray Scattering and Diffraction Intensities 659
10.8.2 The Electron Density Function and the “Phase Problem” 661
10.8.3 Direct Methods 661
10.8.4 Patterson and Symmetry Superposition Methods 662
10.8.5 Least-Squares Refinement 662
10.8.6 Protein Crystallography 663
10.8.7 Liquids, Gases, and Disordered Solids 664
10.8.8 Small-Angle Scattering 665
10.8.9 Diffuse X-ray Scattering 665
10.8.10 Neutron Diffraction 666
10.8.11 EXAFS and XANES 666
10.9 Spectroscopy 667
10.10 Visible–Ultraviolet (V–UV) Spectroscopy 667
10.10.1 Polarization of V–UV Absorption 668
10.10.2 Application: Specular Reflection by Crystal Faces 668
10.10.3 Optical Conductivity 671
10.10.4 Vacuum Ultraviolet Spectroscopy 671
10.10.5 Application: First Excited State of Linear Polyenes 671
10.10.6 Application: Solvatochromism 671
Contents xiii
10.11 Atomic Absorption, Atomic Emission, and Atomic Fluorescence Spectroscopies 672
10.12 Infrared and Near-Infrared Spectroscopy 673
10.12.1 FT-IR Advantages 675
10.13 Raman Spectroscopy 677
10.14 Inelastic Electron Tunneling Spectroscopy 679
10.15 Fluorescence Spectroscopy 682
10.16 Microwave Spectroscopy 683
10.17 Surface Plasmon Resonance 684
10.18 X-ray Photoelectron Spectroscopy (XPS) and Auger Electron Spectroscopy (AES) 684
10.19 Magnetic Measurements 687
10.20 Magnetic Resonance 696
10.20.1 The Family of Magnetic Resonance Techniques 696
10.20.2 Nuclear Magnetic Resonance (NMR) 699
10.20.3 Electron Paramagnetic Resonance (EPR) Spectrometer 699
10.20.4 The Bloch Equations for Magnetic Resonance 701
10.20.5 Slow Passage or Equilibrium or Steady-State Solution 703
10.20.6 Small Magnetic Field: Measurement of T2 705
10.20.7 Measurement of T2 705
10.20.8 Measurement of T1 706
10.20.9 Rapid Passage 706
10.20.10 Free Induction Decay 707
10.20.11 Spin-Echo NMR 708
10.20.12 Selective Saturation 708
10.20.13 NMR Spectrum of Ethanol 709
10.20.14 Chemical Shifts in NMR 709
10.20.15 Multiplets in NMR 710
10.20.16 Paramagnetism Kills the NMR Spectrum by Broadening 711
10.20.17 Magnitude of Relaxation Times 711
10.20.18 NMR in Solids 712
10.20.19 Magic-Angle Spinning 712
10.20.20 Multiple-Pulse Narrowing 712
10.20.21 2D NMR 712
10.20.22 Derivative Detection of EPR Transition 713
10.20.23 Stable Free Radicals 714
10.20.24 g-Tensor 714
10.20.25 Fine-Structure Splittings in ESR Spectra of Triplet States 716
10.20.26 Spin Labeling 716
10.20.27 Nuclear Resonance in Paramagnetic Systems: Knight Shift 717
10.20.28 Overhauser Effect 717
10.20.29 Electron–Nucleus Double Resonance (ENDOR) Spectroscopy 718
10.20.30 Optically Detected Magnetic Resonance (ODMR) 718
10.20.31 Nuclear Quadrupole Resonance (NQR) 719
10.21 Mössbauer Spectroscopy 723
10.22 Electrochemical Methods 727
10.23 Electric Susceptibility 733
10.24 Nonlinear Optical Properties 734
10.25 Ellipsometry 737
10.26 Calorimetry 739
10.26.1 Reaction Calorimeters 741
10.26.2 Constant-Pressure Reaction Calorimeters 741
10.26.3 High-energy Particle Calorimeter 744
References 744
xiv Contents
11 Inorganic Chemistry and Nanomaterials 749

11.1 Periodicity, the Discovery and Abundance of the Chemical Elements, and Valences 750
11.2 Nomenclature 757
11.3 Ionization Energies 757
11.4 Expansion of Acid and Base Concepts 758
11.5 Hard and Soft Acids and Bases 761
11.6 Eighteen-Electron “Rule” 761
11.7 Measures of Radii of Atoms and Ions 762
11.8 Bond Energies 770
11.9 Ionic Radii as a Function of Coordination Number, and Crystal Lattices 774
11.10 Structure and Bonding of Transition Metals 778
11.11 The Virtues of Valence-Bond Theory 778
11.12 The Virtues of VSEPR Theory 780
11.13 The Virtues of Crystal Field Theory 780
11.14 The Virtues of Ligand-Field Theory 785
11.15 The Virtues of Walsh Diagrams 790
11.16 Electron Transfer Theory and Mixed Valence 790
11.17 Mad Romp Through the Periodic Table 791
11.17.1 From Group 1: Hydrogen 791
11.17.2 From Group 1: Alkali Metals 793
11.17.2.1 Flame Test 794
11.17.3 From Group 2: Alkaline Earths 794
11.17.4 From Group 2: Calcium 794
11.17.5 From Group 3: Lanthanoids (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy) and Actinoids (Ac, Th, Pa, U, Np, Pu, Am,
Cm, Bk, Cf, Es, Fm, Md, No, and Lr) 795
11.17.6 From Group 4: Titanium 796
11.17.7 From Group 6: Chromium 796
11.17.8 From Group 6: Manganese 796
11.17.9 From Group 8: Iron 797
11.17.10 Ferromagnetism, Antiferromagnetism, and Ferrimagnetism 799
11.17.10.1 Present Frontier of Flexible Magnetic Media 799
11.17.11 Single-molecule Magnets (SMMs) 801
11.17.12 From Group 10: Platinum 801
11.17.13 From Group 12: Mercury and Superconductivity 801
11.17.14 From Group 13: Boron 801
11.17.15 From Group 13: Aluminum 802
11.17.16 From Group 13: Gallium and Indium 802
11.17.17 From Group 14: Carbon Allotropes 802
11.17.18 Cyclic Oxocarbon Anions 805
11.17.19 Photosynthesis, Oxides of Carbon, and Global Warming 806
11.17.20 From Group 14: Silicon 808
11.17.21 From Group 14: Tin 808
11.17.22 From Group 14: Lead 808
11.17.23 From Group 15: Pnictogens (N, P, As, Sb, Bi, and Mc) 809
11.17.24 From Group 15: Nitrogen 809
11.17.25 From Group 15: Phosphorus 810
11.17.26 From Group 15: Arsenic 812
11.17.27 From Group 16: Oxygen 813
11.17.28 Ozone O3 813
11.17.28.1 Smog 813
11.17.29 From Group 16: Sulfur 814
11.17.30 From Group 16: Polonium 814
Contents xv
11.17.31 From Group 17: Fluorine 814

11.17.32 From Group 17: Chlorine 815
11.17.33 From Group 18: Helium 816
11.17.34 From Group 18: Argon 816
11.17.35 From Group 18: Radon 816
11.17.36 From Group 18: Halides of Noble Gases 817
11.18 Reactions of Inorganic Complexes 817
11.19 Organometallics 819
11.20 Industrial Inorganic Chemistry 819
11.21 Elements Essential to Human Nutrition 821
11.22 Nanomaterials 821
11.23 Nanoparticle Synthesis 822
11.24 Size Dispersion in Nanoparticles 824
11.25 Excitons, Plasmons, and Quantum Dots in Semiconducting Nanoparticles 824
References 827
12 Organic and Polymer Chemistry and Catalysis 833

12.1 Structure and Bonding 835
12.2 Nomenclature 836
12.3 Functional Groups 838
12.4 Optical Activity and Enantiomers 843
12.5 Reactivity of Molecules 847
12.6 Lewis Acids and Bases, Strong and Weak 851
12.7 Resonance 851
12.8 Electron-pair Pushing 851
12.9 Walsh Diagrams 852
12.10 Many Ways of Looking at Thermal or Photochemical Cycloadditions 855
12.10.1 The Diels–Alder Reaction 859
12.11 Polarity of Solutes and Solvents 860
12.12 Trends in Acid Dissociation Constants Explained 860
12.13 Reaction Types 862
12.14 Compendium of Reaction Types 863
12.14.1 SN1 (Substitution, Nucleophilic, Unimolecular) 863
12.14.2 SN2 (Substitution, Nucleophilic, Bimolecular) 869
12.14.3 SN 1 (Substitution, Nucleophilic, Unimolecular, Allylic Rearrangement) 870
12.14.4 SN2 (Substitution, Nucleophilic, Bimolecular, Allylic Rearrangement) 870
12.14.5 SE1 (Substitution, Electrophilic, Unimolecular) 870
12.14.6 SE2 (Substitution, Electrophilic, Bimolecular): E and F are electrophiles 871
12.14.7 SRN1 (Substitution, Radical, Nucleophilic, Unimolecular) 871
12.14.8 SH1 (Substitution, Homolytic, Unimolecular) 872
12.14.9 SH2 (Substitution, Homolytic, Bimolecular) 872
12.14.10 SN2Ar (also Known as SNAr) (Substitution, Nucleophilic, Bimolecular, Aromatic) 873
12.14.11 SE2Ar (Substitution, Electrophilic, Bimolecular, Aromatic) 873
12.14.12 E1 (Elimination, Unimolecular) 873
12.14.13 E2 (Elimination, Bimolecular) 874
12.14.14 E1cB (Elimination, Unimolecular, Conjugate Base) 874
12.14.15 Ei (Elimination, Intramolecular) 874
12.14.16 AdE2 (Addition, Electrophilic, Bimolecular) 875
12.14.17 AdN2 (Addition, Nucleophilic, Bimolecular) 875
12.14.18 AdH2 (Addition, Homolytic, Bimolecular) 876
12.14.19 E-Ad (Elimination, Addition) 877
xvi Contents
12.14.20 BAc2 (Basic Conditions, Acyl Transfer, Bimolecular) 877

12.14.21 AAc2 (Acidic Conditions, Acyl Transfer, Bimolecular) 877
12.15 Molecular Rearrangements 878
12.16 Organometallic Compounds 879
12.17 Catalysis 880
12.17.1 Turnover Number 882
12.18 Linear Free Energy Relationships 889
12.19 Retrosynthetic Analysis 890
12.20 Stable Free Radicals 891
12.21 Organic Polymers 893
12.22 Protecting Groups 897
12.23 Environmental Concerns 897
List of Named Organic Reactions 897
References 913
13 Biochemistry 923
13.1 Cells and Cell Walls 924
13.2 Amino Acids and Oligopeptides 928
13.3 Peptides and Proteins 931
13.4 Enzymes 936
13.5 Chymotrypsin 938
13.6 Lysozyme 939
13.7 Carbohydrates and Glycoproteins 941
13.8 The Immune System 944
13.9 Nucleotides, Nucleic Acids, DNA, and RNA 946
13.10 Gene Expression from DNA to RNA Yields Polypeptide Assembly on a Ribosome 950
13.11 DNA Replication 953
13.12 DNA Manifold Replication, Clones and the Genome 955
13.13 Bio-energetics I: AMP, ADP, and ATP 958
13.14 Bio-energetics II: Anaerobic Glycolysis 960
13.15 Bio-energetics III: Citric Acid (or Krebs) Cycle 962
13.16 Vitamins 964
13.17 Oxidative Phosphorylation 964
13.18 Photosynthesis and Photophosphorylation 964
13.19 Neurons, the Nervous System, and the Human Brain 970
13.20 Parting Thoughts 975
References 976
End-of-Chapter-Problems 976
Index 979
xvii
Foreword
This book is exceptional, likely unique, for both the breadth of its coverage and the depth of the presentation. It is much
more than a textbook of physical chemistry. It is a compendium of physical science, that somehow manages to present all
relevant subjects, from particle physics and general relativity to life science, in full mathematical detail. The book assumes
little knowledge, even of the mathematical tools, for which it provides complete instruction and examples. It is a must-have
book, not only for students but also for practicing scientists in a wide range of disciplines.
The book belongs to a great tradition of physical chemistry, which originated in statistical physics and quantum mechan-
ics over a hundred years ago, and which has led to the “toolbox” of the book title. Application of these “tools” has led to
discoveries in chemistry, life science, and medicine. The trajectory from quantum mechanics to medicine was personified by
Linus Pauling, a towering figure of twentieth century chemistry. Pauling defined the path from “the nature of the chemical
bond” to principles of protein structure to molecular medicine. The author of this book was a student of Harden McConnell,
an acolyte of Pauling. The broad sweep of the book from quantum chemistry to biochemistry and the rigor of the presen-
tation are legacies of Pauling and the great century of physical science.
The book will, I hope, help sustain these legacies against the countervailing pressures of the modern, information age. It
was once possible to be a generalist and maintain an active, meaningful interest in all areas of science. Pauling could address
important questions ranging from atomic physics to medicine. Today, with the proliferation of information, it is difficult to
keep abreast of developments in even one narrow slice of one research area. The joy of science, the possibility of pondering
and even understanding all of nature, is much diminished.
As attention becomes focused on information, there is a tendency toward superficiality. There is less interest in discover-
ing fundamental principles. The book pushes back against this unfortunate tendency, by deriving much of chemistry from
first principles. Students and active scientists alike may be influenced to seek the underlying basis of things.
This book therefore goes beyond instruction in physical chemistry to a kind of manifesto of science. It nurtures a broad
interest and a desire to unravel the mysteries of nature. Despite all that has been learned, these mysteries abound. I, for one,
will carry this book as a companion, for both source and stimulation. I hope a generation of young physical chemists will do
the same.
Roger D. Kornberg
Stanford
14 December 2022
xix
Preface and Philosophy
“Felix qui potuit rerum cognoscere causas”

=Happy is he who could know the causes of things
[Publius Vergilius Maro, 79 BC–19 BC, Georgics, Book 2 line 490]
“Provando e riprovando” (= test and test again)
Motto of the Accademia del Cimento (founded in Florence, Italy 1657)
“Fram” (= Norwegian for ”Forwards” = the name given to his ice-breaking ship by the
Arctic explorer and humanist Fridjof Nansen (1861–1930))
“Never give in. Never give in. Never, never, never, never, never give in.”
[Sir Winston Churchill (1874–1965) at Harrow School, 29 October 1941]
Ten years have elapsed since the First Edition of this book was published in 2012. It fared reasonably well as a compendium,
or encyclopedic review of theories and experiments in physics and chemistry, but it failed miserably as a textbook: almost no
classroom adoptions. This Second Edition is trying to help fix shortcomings, and add new material.
As before, the intended audience for this Toolbox remains the beginning researcher, who often has difficulty in reconcil-
ing recent or past classroom knowledge in the undergraduate or first-year graduate curriculum with the topics and research
problems current in research laboratories in the twenty-first century.
While several excellent and specialized monographs do exist for all the topics discussed in this book, to my knowledge
there is no single book, that covers adequately the disparate techniques needed for scientific advances in the twenty-first
century. In particular, there is a need to find “what will this or that technique do for my research problem?” The aim of this
Toolbox is therefore fourfold:
1) summarize common bases of mathematics, physics, chemistry, and materials science,

2) explain topics and techniques that underpin scientific instruments,
3) discuss the advanced instrumentation available in research,
4) review inorganic and organic chemistry, and biochemistry.
The book is interspersed with problems to do: some trivial, some difficult. This keeps the volume more compact, and
should be a useful pedagogical tool. This book tries to be a mathematically deep, yet brief and useful compendium of several
topics, which can and should be covered by more specialized books, courses, and review articles.
Throughout, the aim is to bring the student up to speed. The teaching of chemistry leaned rather heavily toward math-
ematical and physical rigor in the 1960s, but this fervor may have diminished, as chemical, physical, and biochemical com-
plexity eluded simple mathematical precision, and quite often the true answers would appear as small differences between
large numbers.
Lamentably, the recent educational trend has been to train what could be called one-dimensional scientists, very good in
one subfield, but blissfully unaware of the rest. It is sad that we no longer produce those broadly trained scientists of past
generations, who were willing to delve into new problems far from their original interest: I am thinking of Hans Bethe, Peter
Debye, Enrico Fermi, Linus Pauling, or Edward Teller. This Toolbox tries to adhere to this older and broader tradition,
redress the temporary malady, and help restore the universality of scientific inquiry.
Since 1936, The American Chemical Society has had a very successful Committee on Professional Training, that monitors
the classroom and laboratory preparation of undergraduates with a declared major in “ACS-certified” bachelor’s program.
xx Preface and Philosophy
Unfortunately no such monitoring exists for doctoral programs in chemistry, mainly because the thrust of the faculty direct-
ing doctoral dissertations is to minimize the academic course load, and maximize the time a student will work on their
doctoral research.
As Professor Marshall Oneillon of the University of Wisconsin explained to me, the research productivity of any student
might be estimated by a simple multiplication factor (MF). A mere data taker would be for his/her professor or research
advisor MF = 1.0: the professor could have collected the data himself or herself. A more creative or better-prepared graduate
student would be an MF > 1.0 (not easy to quantify). Research groups with a cumulative MF much greater than 1.0 would be
a tremendous resource to the research advisor, who could undertake higher-impact research projects. Immodestly, I will
claim that any student mastering the contents of the present textbook would raise his/her MF.
To the instructor: This Toolbox could be taught in a one-year graduate course covering in fair depth the concepts and
methods of physical, analytical, inorganic, and organic chemistry and also biochemistry, plus elements of materials science
and solid-state physics. This course could be team-taught. It should be taught with mandatory problem sets (students will
connect the dots by doing the suggested problems), and with recourse to traditional texts that cover e.g. quantum mechanics
or statistical mechanics in much greater detail. I am reminded of the very successful one-year team-taught courses such as
“Western Civilization” at Stanford University in the 1960s! I have taught selected chapters of the First Edition of the Toolbox
several times at the University of Alabama as a one-semester course.
To guide the student toward the more important equations, these are enclosed in thin black rectangles. In some chapters,
the more arcane topics are relegated to Special Topics (ST) sections, which are enclosed in large rectangles with pale blue
titles. To help with the teaching, PowerPoint® lectures that mirror the text are provided in the Supplementary Material. The
problems are shown with a gray background. Answers to all problems are in the Supplementary Material. Relevant anec-
dotes and some personal recollections are interspersed with the text to lighten the tone and interrupt the monotony of too
many serious concepts.
To Chemistry and Physics departments: The Toolbox could become a valuable resource for all entering graduate students,
so maybe students, even in areas far from physical chemistry, should be encouraged to buy it and work at it on their own.
To the student: (i) Do the problems; (ii) read around in specialized reference texts that may be suggested either in this
Toolbox or by your instructor(s); (iii) discover whether the Toolbox could be developed in new directions; (iv) my apologies
to you if long Tables were placed within the text as soon as they were mentioned, instead of relegating them to appendices at
the end of chapters: I hope that you do not fall asleep, but learn to skip over these Tables; (v) you could use my book as a
doorstop.
To myself: To adapt Tom Lehrer’s (1928–) famous quip, I am embarrassed to realize that at my present age Mozart had
been dead for 36 years.
Alan MacDiarmid (1927–2007) once said “Chemistry is about people”: In this spirit, full names and birth and death dates
are given to all the scientists quoted in this book; such brief historical data may help illuminate how and when science was
done. I have resisted mentioning who was a Nobel prize winner: too many to list, and some worthy scientists, e.g. Mende-
leyeff, Eyring, Edison, Slater, and Tesla, were not honored.
I owe a deep debt of gratitude to many people who have educated me over several decades, as live teachers and silent
authors. In particular I am indebted to Prof. Willard Frank Libby (1908–1980), who taught us undergraduates at UCLA
to love current research problems, and led us into quite a few wild-goose chases; Prof. Harden Marsden McConnell
(1927–), who led us at Caltech and Stanford by example to see what are the interesting problems and what are “trivial”
problems; Prof. Linus Carl Pauling (1901–1994), who taught me electrical and magnetic susceptibilities with his incompa-
rable photographic recall of data and dates, and with his insight and humanity about current events; Dr. Richard Edward
Marsh (1922–2017) and Prof. Paul Gravis Simpson (1937–1978), who taught me crystallography; Prof. Michel Boudart
(1925–2012), who introduced me to heterogeneous catalysis; Mr. William D. Good (1937–1978), who taught me combustion
calorimetry; Prof. Sukant Kishore Tripathy (1952–2000) who introduced me to Langmuir–Blodgett films, and finally,
Prof. Richard Phillips Feynman (1918–1983), who taught me about the Schwarzschild singularity and event horizons,
and who was a source of deep inspiration, pleasant conversations, and mischievous fun. Thanks are also due to two persons
who helped me greatly in my academic career, and taught me a thing or two about what good science really means: Prof.
Andrew Peter Stefani (1927–2014) of the University of Mississippi and Prof. Michael Patrick Cava (1926–2010) of the Uni-
versity of Alabama. Prof. Carolyn J. Cassady (University of Alabama) kindly allowed me to use an experiment she had
devised for students of mass spectrometry.
The following books have inspired me: (i) Principles of Modern Physics, by Robert B. Leighton, (ii) Theoretical Physics by
Georg Joos, (iii) The Feynman Lectures on Physics by Richard P. Feynman, (iv) Principles of Instrumental Analysis by Doug
Preface and Philosophy xxi
Skoog, James Holler, and Stanley Crouch. In this twenty-first century, much help was obtained on-line from Wikipedia, but
“caveat emptor”!
Writing is teaching but also learning; with Marcus Porcius Cato (234–149 BC) who was echoing Solon (630–560 BC), I dare
to say again: “senesco discens plurima.”
Thanks are due to several friends and colleagues, who corrected errors and oversights: Prof. Massimo Carbucicchio
(University of Parma, Italy), Profs. Michael Bowman, Dan Goebbert, Shanlin Pan, and Richard Tipping (University of
Alabama), Prof. Harris J. Silverstone (Johns Hopkins University), Professor Zoltán G. Soos (Princeton University),
Dr. Ralph H. Young (Eastman Kodak Co.), Adam Csoeke-Peck (Brentwood, California), and Prof. Joel Primack (University
of California Santa Cruz). Prof. Silverstone also helped me with some graphics. A fellow group member of the McConnell
lab at Stanford, Prof. Roger Kornberg (Stanford University) agreed to write a Foreword.
The errors that remain are all mine; errare humanum est, sed perseverare diabolicum [Lucius Anneus Seneca (c. 4 BC–66 AD)].
To the reader who finds errors: my apologies: I will try to correct the errors for some next edition; echoing what Akira
Kurosawa (1910–1998) said in 1989, when he received an honorary Oscar for lifetime achievements in cinematography:
“So sorry, [I] hope to do better next time.” And if a new edition must be done, in 10 years I will be 92 years old! I tell people
that with good luck your body parts are warranted for 60 years; between the ages of 60 and 80 you are on extended warranty;
beyond the age of 80, good luck!
COVID-19 became a deadly pandemic for the whole world; for me it caused a frustrating delay: although I had sent the
finished manuscript to my publisher, Wiley/VCH in June 2020, as I was retiring at age 80 from the University of Alabama,
nothing was done for more than one year. The proof-reading and typesetting was done in Chennai, India, and I owe an
immense debt of gratitude to Mrs. Viniprammia Premkumar and Mr. Kavin Shanmughasundaram for their hardwork,
patience, thoroughness, love of detail, and infinite courtesy. Hopefully the book should be ready for shipment and sale
next year.
Robert M. Metzger
Department of Chemistry and Biochemistry, The University of Alabama
Tuscaloosa and Birmingham, Alabama, USA
15 November 2022
xxiii
About the Companion Website
This textbook is supported by a website which contains a variety of supplementary resources:
www.wiley.com/go/metzger/physchemtoolbox2
Online you will find:

1) Answers to almost all the problems
2) Chart of the Nuclides
3) Powerpoint lectures for all chapters
1
Fundamental Particles, Fundamental Forces, and Mathematical Tools
“Viribus Unitis”
[with united forces]
Emperor Franz Josef the First (and the last) (1830–1916)
“It is difficult to make predictions, especially about the future”

Lawrence P. “Yogi” Berra (1925–2015)
1.0 Introduction
This chapter presents several principles that underpin the chemical edifice; it is divided into four parts (Julius Caesar’s Gaul
was divided into only 3 parts). Part One (Sections 1.1–1.4) presents the fundamental physical forces whose interplay underlie
Mendeleyeff’s1 periodic table of the chemical elements. Part Two (Sections 1.5–1.8) reviews essential mathematical meth-
ods. Part Three (Section 1.9) discusses electricity and magnetism. Part Four (Sections 1.10–1.18) discusses the meaning of
quantum numbers, special relativity, general relativity, Feynman diagrams, physical optics, mathematical transforms, con-
tour integration, and statistics.
The chapter concludes with eleven Special Topics: 1. Natural Linewidths; 2. Nuclear Shell Model; 3. Factoring a Polyno-
mial; 4. Other Solutions of the Cubic Equation; 5. Solving a Quartic Equation; 6. Spherical Trigonometry; 7. Unit Systems for
Electromagnetism; 8. Nonlinear Optics; 9. Conic Sections, Ellipses, and Planetary Motion; 10. Ellipsometry in Detail; 11:
Standard Model, The Eightfold Way.
Within a traditional textbook, these concepts and methods would be presented as needed, but it seemed expedient to pull
them together here: this is a deliberate effort to link mathematics, physics, and chemistry into a unified and coherent whole.
In this book, important equations are boxed. To save space at the cost of elegance, fractions are mostly replaced by neg-
ative exponents for the denominator. For emphasis, double parentheses are used for those equations that had been pre-
sented earlier in the text.
To relieve the reader from too much seriousness. Sidelines occasionally interrupt the narrative.
Sideline 1.1 The name “physics” derives from the Greek word ϕυσις (=nature, essence): early physicists like
Newton2 were called natural philosophers. The word “chemistry,” through its Arabic precursor alchimya, derives
from the Greek word χημι (=black Earth), a tribute to the Egyptians’ embalming arts. Mathematics comes from
the Greek μαθημα (=learning, study). Algebra comes from the Arabic al-jabr (=transposition [to the other side of
an equation]). Calculus (as in “infinitesimal calculus”) is the Latin word for a small pebble.
1 Dmitri Ivanovich Mendeleyeff (1834–1907).

2 Sir Isaac Newton (1642–1727).
The Physical Chemist’s Toolbox, Second Edition. Robert M. Metzger.

© 2023 John Wiley & Sons, Inc. Published 2023 by John Wiley & Sons, Inc.
Companion website: www.wiley.com/go/metzger/physchemtoolbox2
2 1 Fundamental Particles, Fundamental Forces, and Mathematical Tools
Sideline 1.2 Michael Faraday3 was asked “Of what use is electricity?” He supposedly answered “What is the use of a
new-born baby?” This same answer was actually first given by Franklin4 when witnessing the flight of the Montgol-
fier balloon over Versailles in 1785; this answer was repeated by Faraday in 1816 a propose of the discovery by Sir
Humphry Davy5 of several new chemical elements.
PART ONE: Fundamental Forces
1.1 Fundamental Forces, Elementary Particles, Nuclei, and Atoms
In a freshman chemistry class at the University of California, Los Angeles, in 1959, the instructor, Libby,6 defined chemistry
as “the study of electrons and what they do.” However, he took pains to teach us that these electrons would have “nothing to
do if atomic nuclei did not exist.” So, it behooves us to talk briefly about nuclei, elementary particles, and the fundamental
forces in the cosmos: this will put chemistry in its proper perspective.
Sideline 1.3 Willard Libby told his physical chemistry class in 1960 “if you want to find out the science that is ten
years old, read a book; if you want to find out what is five years old, read a review article; if you want to find out what
is one year old, read a scientific article; if you want to find what is current today, pick up the telephone.”
The four fundamental forces, their governing equations, the mediating particles, their relative magnitudes, and their
ranges are listed in Table 1.1.
For some chemists and materials scientists, only the electrical force is considered essential, so much of Table 1.1 may
seem esoteric. But stable atoms exist only if the relevant nuclei can survive: chemists ignore nuclei at their own peril.
For some elementary particle experimentalists, most of everything “at lower energies” (below 1 GeV) is jocularly described
as “chemistry.” Astronomers try to observe and explain the whole universe, so they must worry about everything, starting with
gravitation and ending in nuclear structure and chemistry! The known elementary particles are listed in Tables 1.2 and 1.3.
We now introduce the four fundamental forces.
Force one: The first (and weakest) force is Newton’s force of universal gravitation (1687) [1.1]:
F 12 = − Gm1 M 2 r 12 r 312 111
which describes the attractive force F12 between two bodies of masses m1 and M2 placed a distance r12 apart, where G is the
constant of gravitation. The largest visible objects in the universe (galaxies, stars, quasars, planets, satellites, comets) are
Table 1.1 The fundamental forces.
Force Law Equation Mediating particle Relative magnitude Range
Gravitation Newton’s F 12 = − Gm1 M 2 r 12 r 312 Graviton 10−39 Infinite

a −2
Electricity Coulomb’s F 12 = q1 q2 r 12 4πε0 r 312 Photon 10 Infinite
−5
Weak nuclear — — Vector boson 10 10−18 m
Strong nuclear Inter-quark — Gluon b
1 10−15 m
Strong nuclear Inter-nucleon — Pion (gluon?)b 1 10−15 m
a
Charles-Augustin de Coulomb (1736–1806).
b
For nucleon–nucleon strong interactions within nuclei, pions (=two-quark particles; see below) may be the mediating particles: gluons are
probably not involved directly, since the nucleons have no “color charge.” The internucleon potential goes to zero beyond 1.7 fm = 1.7 × 10−15 m.
Source: Adapted from Serway [1.3].
3 Michael Faraday (1791–1867).

4 Benjamin Franklin (1706–1790).
5 Sir Humphry Davy (1778–1829).
6 Willard Frank Libby (1908–1980).
Table 1.2 Fundamental (quark, gluon, graviton, neutrino) and elementary (=fundamental plus two-quark and three-quark combinations) particles.
Relative
Life-time Relative electric Spin Parity Isospin z-component Baryon Strangeness Charm Beauty Truth
Particle name Symbol τ (sec) mass m charge Q S P T Isospin Tz Ba St Ch By Tr Composition
Quarks (fundamental, with six “flavors” u, d, s, c, b, and t, but not observed as single particles):
Up quark u ∞? ~4.6 2/3 1/2 +1 1/2 +1/2 1/3 0 0 0 0
Anti-up quark∗ u ∞? ~4.6 −2/3 1/2 −1 1/2 +1/2 −1/3 0 0 0 0
Down quark d ∞? ~16 −1/3 1/2 +1 1/2 −1/2 1/3 0 0 0 0
Anti-down quark∗ d ∞? ~16 1/3 1/2 −1 1/2 −1/2 −1/3 0 0 0 0
Charmed quark c ∞? ~2490 2/3 1/2 +1 0 0 1/3 0 +1 0 0
Anticharmed q∗ c ∞? ~2490 −2/3 1/2 −1 0 0 −1/3 0 −1 0 0
Strange quark s ∞? ~200 −1/3 1/2 +1 0 0 1/3 −1 0 0 0
Anti-strange q∗ s ∞? ~200 1/3 1/2 −1 0 0 −1/3 +1 0 0 0
Bottom quark b ∞? ~8480 −1/3 1/2 +1 0 0 1/3 0 +1 0 0
Antibottom q∗ b ∞? ~8480 1/3 1/2 −1 0 0 −1/3 0 −1 0 0
Top quark t ∞? >3.4E5 2/3 1/2 +1 0 0 1/3 0 0 0 +1
Antitop quark∗ t ∞? >3.4E5 −2/3 1/2 −1 0 0 −1/3 0 0 0 −1
Fundamental interaction carriers (for gluons, combination of color [r, y, b] and anticolor):
Photon ν ∞ 0 0 1 −1 1,0 1,0 0 0 0 0 0
Vector boson W+ 3E-25 1.6E5 1 1 −1 1 1 0 0 0 0 0
Vector boson Z0 3E-25 1.8E5 0 1 −1 1 0 0 0 0 0 0
Vector boson W− 3E-25 1.6E5 −1 1 −1 1 −1 0 0 0 0 0
Gluon1 rg ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon2 rb ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon3 gb ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon4 gr ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon5 br ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon6 bg ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon7 rr − gg 2 ? 0 0 1 −1 0 0 0 0 0 0 0
Gluon8 rr + gg 0 0 1 −1 0 0 0 0 0 0 0 0
− 2 bb 6
(Continued)
Table 1.2 (Continued)
Relative
Life-time Relative electric Spin Parity Isospin z-component Baryon Strangeness Charm Beauty Truth
Particle name Symbol τ (sec) mass m charge Q S P T Isospin Tz Ba St Ch By Tr Composition
Electron neutrino νe ∞ 0 0 1/2 −1 0 0 0 0 0 0 0

Electron νe ∞ 0 0 1/2 1 0 0 0 0 0 0 0
antineutrino∗
Muon neutrino νμ ∞ 0 0 1/2 −1 0 0 0 0 0 0 0
Muon νμ ∞ 0 0 1/2 1 0 0 0 0 0 0 0
antineutrino∗
Tau neutrino νT ∞ 0 0 1/2 −1 0 0 0 0 0 0 0
Tau antineutrino∗ νT ∞ 0 0 1/2 1 0 0 0 0 0 0 0
Graviton G 0? 0 0 2 ? 0 0 0 0 0 0 0
Higgs boson H0 1.6E-22 >224 0 0 1 0 0 0 0 0 0 0
Leptons (elementary particles):
Electron e−, β−1 ∞ 1 −1 1/2 — — — 0 —
Positron∗ e +, β + ∞ 1 +1 1/2 — — — 0 —
Muona μ− 2.2E-6 237 −1 1/2 — — — 0 —
Positive muon∗ μ+ 2.2E-6- 237 +1 1/2 — — — 0 — —
Tau τ− <4E-13 3477 −1 1/2 — — — 0 — —
Positive Tau∗ τ+ <4E-13 3477 +1 1/2 — — — 0 — —
Mesons (combinations of two quarks):
Positive pion π+ 2.6E-8 273 1 0 −1 1 +1 0 0 0 0 0 ud
Negative pion∗ π− 3E-8 273 −1 0 −1 1 −1 0 0 0 0 0 ud
Neutral pion π0 8E-17 264 0 0 −1 1 0 0 0 0 0 0 uu − dd 2
Neutral ρ meson ρ0 5E-24 1510 0 0 −1 0 0 0 0 0 0 0 uu + dd 2
Positive kaon K+ 1.2E-8 493.8 1 0 −1 1/2 1/2 0 1 0 0 0 us
Negative kaon∗ K− 1.2E-8 493.8 −1 0 −1 1/2 −1/2 0 −1 0 0 0 us
Neutral kaon K0 8.9E-8 493.8 0 0 −1 1/2 −1/2 0 1 0 0 0 ds
Neutral kaon∗ K
0 5.2E-8 493.8 0 0 −1 1/2 1/2 0 −1 0 0 0 ds
η meson η0 5E-19 549 0 0 −1 0 0 0 0 0 0 0 uu + dd − 2ss 6
η meson η 3E-21 958 0 0 −1 0 0 0 0 0 0 0 uu + dd + ss 3
Hadrons or Baryons (combinations of three quarks):
Proton p, 1p1 ∞ 1838 +1 1/2 1 1/2 +1/2 1 0 0 0 0 uud
Anti-proton∗ p− ??? 1838 −1 1/2 1 1/2 +1/2 −1 0 0 0 0 uud
Neutron n, 0n1 925 1839 0 1/2 1 +1/2 −1/2 1 0 0 0 0 udd
Lambda 0
Λ0 2.6E-10 1116 0 1/2 +1 0 0 1 −1 0 0 0 uds
Charm Lambda+ Λc+ 2.0E-13 1116 1 1/2 +1 0 0 1 0 1 0 0 udc
Bottom Lambda0 Λb0 1.4E-12 5622 0 1/2 +1 0 0 −1 0 0 1 0 udb
Sigma+ Σ+ 8E-11 1189 1 1/2 +1 1 1 1 −1 0 0 0 uus
Sigma 0
Σ0 6E-20 1192 0 1/2 +1 1 0 1 −1 0 0 0 uds
Sigma− Σ− 1.5E-10 1197 −1 1/2 +1 1 −1 1 −1 0 0 0 dds
Ch. Sigma2+ Σ 2+ 3.0E-22 1200 2 +1 1 −1 1 −1 1 0 0 uuc
Xi0
Ξ0 2.9E-10 1315 0 1/2 +1 1/2 +1/2 1 −2 0 0 0 uss
Xi− Ξ− 1.6E-10 1321 −1 1/2 +1 1/2 −1/2 1 −2 0 0 0 dss
Omega− Ω− 1.6E-10 1672 −1 3/2 +1 0 0 1 −3 0 0 0 ssb
−31 −2
The masses m are rest masses, quoted relative to the mass of the electron, me = 9.109 389 7 × 10 kg, whose rest-mass energy is 0.510 999 06 MeV c ; the charges Q are quoted relative to the absolute
value of the charge on the electron, e = 1.602 176 57 × 10−19 C; lifetime is given as the known half-life (s) in the abbreviated format 2.34E-3, which translates as τ = 2.34 × 10−3 s; the lifetime is given as infinite
for those particles which have infinite lifetimes (except in particle-antiparticle collisions). “Quark comp.” gives the composition of the elementary particle in terms of its presumed quark components.
Not all unstable hadrons or mesons are listed. Antiparticles to other listed particles are indicated by asterisks (∗), but not all antiparticles are listed. The quantum numbers are for relative charge (Q),
spin (S), parity (P), isospin (T), z-component of isospin (Tz), baryon number (Ba), strangeness (St), charm (Ch), beauty or bottomness (By), and truth or topness (Tr).
a
The muons were first called mu-mesons, but are now better known as muons, leaving the π mesons, or pions, as the particles which may help “carry” the inter-nucleon strong force.
Source: Data from Serway [1.3].
Table 1.3 Standard model of elementary particles.
Three historical generations of fermions

bosons
I II III
m = 2.2 MeVc–2 m = 1.28 MeVc–2 m = 173 MeVc–2 m=0 m =125 GeV c–2
Q = 2/3 Q = 2/3 Q = 2/3 Q=0 Q=0
Spin = 1/2 Spin = 1/2 Spin = 1/2 spin = 1 spin = 0
3 colors: R,B,G 3 colors: R,B,G RB’, and 7 more
3 colors: R,B,G
u c t g H
up charm top
Quarks
gluon Higgs
m = 4.7 MeVc–2 m = 96 MeVc–2 m = 4.18 MeVc–2

Q = –1/3 Q = –1/3 Q = –1/3 m=0
Spin = 1/2 Spin = 1/2 Spin = 1/2 Q=0
3 colors: R,B,G 3 colors: R,B,G 3 colors: R,B,G Spin = 1
d s b γ
down strange bottom photon
m = 0.51 m = 105.66
Gauge bosons
m = 1.7768 m = 91.9
MeVc–2 MeVc–2
Scalar boson
GeVc–2 GeVc–2
Q = –1 Q = –1 Q = –1 Q=0
Spin = 1/2 Spin = 1/2 Spin = 1/2 Spin = 1
e μ τ Z
electron muon Z boson
tau
Leptons
m < 2.2eV c–2 m < 1..7MeV c–2 m = 80.39

m < 15.5MeV c–2
Q=0 Q=0 GeV c–2
Q=0
Spin = 1/2 Spin = 1/2 Q = ±1
Spin = 1/2
νe νμ ντ Spin = 1
electron muon tau W
neutrino neutrino neutrino W boson
Note that “gauge” is a misnomer for “phase.”
held together by this weakest force, which may be transmitted by a mediating particle called the graviton (first detected in
2016) [1.2]. Its range extends to the whole universe. Masses are always positive.
Force two: it is the electrical force, which obeys Coulomb’s law (1785) [1.4]:
F 12 = q1 q2 r 12 4πε0 r 312 112
which describes the attractive (or repulsive) force F12 between two electrical charges q1 and q2 (positive or negative) placed
r12 apart, where ε0 is the electrical permittivity of vacuum. The fundamental electrical monopole (electron) is probably infi-
nitely stable; the mediating particle for the electrical force (photon) is observed and well understood. Magnetism is usually
due to moving electrical charges, but its monopole has never been seen, so magnetism is not really an independent force;
atoms have magnetic properties, and in wires the gegenions of electrical currents are dealt with as if they were “stationary,”
yet the overall charge is zero: hence, incredible dictu, magnetism is a special relativistic effect. As explained in Section 2.9,
electricity and magnetism are well described by Maxwell’s7 four field equations [1.5].
Force three: it is the “weak nuclear” or “Fermi”8 force (1934) [1.6], which explains the “β decay” of unstable nuclei into
stable ones and positron emission. The positron (β+ or e+) is the antiparticle of the electron (e−);
Force four: it is the strongest force in the universe; it is the “strong nuclear force,” which binds together the nuclei
and the constituents of atomic nuclei, but has an extremely narrow range. Indirect experimental evidence exists for a
mediating particle (gluon). Nucleons (neutrons, protons) and maybe also all nuclei consist of “elementary” particles
7 James Clerk Maxwell (1831–1879).

8 Enrico Fermi (1901–1954).
Table 1.4 Fundamental constants (gram-mole = molar mass in grams).
Name Symbol SI value
Gravitational constant G 6.673 84 × 10−11 m3 kg−1 s−2

Rest mass of electron me 9.109 389 7 × 10−31 kg
Electrical charge of electron e −1.602 176 57 × 10−19 C
Speed of light c 2.997 924 58 × 108 m s−1
Planck’sa constant of action h 6.626 070 15 × 10−34 J s
Planck’s reduced constant of action ℏ ≡ h/2π 1.054 571 6 × 10−34 J s
Free electron g-factor ge 2.002 319 304 386
Avogadro’sb number NA 6.022 140 76 × 1023 molecules(gram - mole)−1
Gas constant R 8.314 462 2 J mol−1 K−1
a
Max Planck (1858–1947).
b
Lorenzo Romano Amedeo Carlo Bernadette Avogadro, Conte di Quaregna e Cerreto (1776–1856).
Source: Modified from Mohr et al. [1.7].
Table 1.5 Other constants.
Name Symbol Equation SI value
Sommerfelda fine-structure constant α = e2/2ε0ch 1/137.035 999(=e2/ℏc in esu)

Gravitational acceleration at sea level at Equator g 9.780 31 m s−2
b
Boltzmann constant kB = R/NA 1.380 648 8 × 10−23 J K−1
Electrical permittivity of vacuum ε0 = m0− 1 c − 2 8.854 187 817 × 10−12 F m−1
−7
Magnetic permeability of vacuum μ0 = 4π10 1.256 637 061 4 × 10−6 N A−2
von Klitzingc–Landauerd quantum of resistance R0 = he−2 25 812.807 443 Ω
Magnetic flux quantum Φ0 = h/2e 2.067 833 76 × 10−15 Wb
a
Arnold Johannes Wilhelm Sommerfeld (1868–1951).
b
Ludwig Boltzmann (1844–1906).
c
Klaus von Klitzing (1940–).
d
Rolf William Landauer (1927–1999).
Source: Modified from Mohr et al. [1.7].
called quarks, which have never been seen free (proton–proton scattering experiments do show that protons consist of
“lumps”: this may have been the first experimental evidence for quarks).
Sideline 1.4 The name “quark” comes from a sentence in Joyce’s9 Finnegan Wake; a free quark has never been
isolated, but physicists have not looked in German grocery stores, where Quark is a well-known soft cheese!
Some important constants are given in Tables 1.4 and 1.5.

Other constants and unit conversions are given in Tables 1.6–1.12. The known nuclides are listed in Table X1 (please refer
www.wiley/go/metzger/physchemtoolbox2). We next discuss in more detail gravity, the weak force, and the strong force.
The electrical force is delayed to Part Three (Section 1.9) until after a mathematical interlude is given in Part Two (Sections
1.5–1.8).
9 James Augustine Aloysius Joyce (1882–1941).

Table 1.6 SI base unitsa.
Name Symbol Unit Abbreviation
Length L meter m
Mass M kilogram kg
Time T second s
Electric current J ampère A
Temperature t Kelvin K
Amount of substance mole mol
Luminous intensity candela cd
a
Definitions: 1 m ≈ 1/40 000 000 of circumference of Earth (1790 definition) = 1 650 763.73 wavelengths of the orange-red line of
86
Kr under specified conditions (1960 definition); 1 s = 1/86 400th of a mean Earth day; 1 kg ≈ mass of 1000 cm3 of H2O at 4 C
and 1 atm (1790 definition) = mass of a standard Pt–Ir alloy cylinder in Sèvres, France; 1 A = constant current which, if maintained
in two infinitely long wires of negligible cross section and held parallel 1 m apart in vacuum, would exert a force of 2 × 10−7 N per m
of length.; 1 mol = Avogadro’s number of molecules = 6.022 140 76 × 1023 molecules (gram-mole)−1 = number of molecules per
gram (NOT kilogram!); 1 cd = luminous intensity in the perpendicular direction of a surface of 1/600 000 of a square meter of a
blackbody at 1773 C and 1 atm (older definition) = luminous intensity in a given direction of a source of monochromatic radiation of
frequency 5.40 × 1014 Hz and that has a radiant intensity in that direction of 1/683 W sr−1 (1979 definition).
Table 1.7 Metric multipliers: tera, peta, exa come from tetra, penta, hexa with one letter removed; zetta, yotta come from
zeta, iota, with one letter added; atto comes from Danish “atten” for 18; zepto comes from Latin “septem” or Greek “hepta”
(1000−7); and yocto comes from Greek “octo” (1000−8) with one prefix letter added.
deca da ×10+1 deci d ×10−1

hecto h ×10 +2
centi c ×10−2
kilo k ×10+3 milli m ×10−3
mega M ×10 +6
micro μ ×10−6
giga G ×10+9 nano n ×10−9
tera T ×10 +12
pico p ×10−12
peta P ×10+15 femto f ×10−15
exa E ×10 +18
atto a ×10−18
zetta Z ×10+21 zepto z ×10−21
yotta Y ×10 +24
yocto y ×10−24
Table 1.8 Atomic units (using SI values for e, me, h, c).
Quantity Description Symbol Size (in SI units)
Charge Charge of the electron e −1.602 176 57 × 10−19 A s

Speed Speed of light in vacuum c 2.997 924 58 × 108 m s−1
Velocity Velocity of electron in first Bohr orbit e2/2ε0h 2.1877 × 106 m s−1
Mass Rest mass of the electron me 9.109 389 7 × 10−31 kg
Length Radius of first Bohr orbit (1 b = a0) 107 h 2πec 2 me− 1 5.291 772 5 × 10−11 m
Time (From electron momentum in first Bohr orbit) 2e20 h3 πme e4 2.4189 × 10−17 s
Gravitation Newton’s constant of universal gravitation G 6.673 × 10−11 m3 kg−1 s−1
Energy 2×H atom ionization energy (1 hartree) me e4 4e20 h2 4.3558 × 10−18 J
Momentum Electron momentum in first Bohr orbit mee2/2e0h 1.9926 × 10−24 kg m s−1
Quantity Description Symbol Size (in SI units)
Frequency (From electron momentum in first Bohr orbit) πmee4/2ε0h3 4.1341 × 1016 s−1
Electrical potential (From electron momentum in first Bohr orbit) 3 2 27.210 V
π1 2 me e3 2ε0 h2
Electrical field (From electron momentum in first Bohr orbit) π 2
m2e e4 ε20 h4 5.142 × 109 V cm−1
strength
h Planck’s constant (of action) h 6.626 069 0 × 10−34 J s
ε0 Electron permittivity of vacuum (artificial) 10 /4πc 7 2
8.853 742 338 × 10−12 F m−1
(use this number for SI unit
conversions; otherwise units:
s2 m−2)
μ0 Magnetic permeability of vacuum (artificial) 4π10−7 1.256 637 061 4 × 10−6 N A−2
(use this for SI unit conversions;
otherwise, pure number; also:
H m−1)
Table 1.9 Other derived constants (using SI values for e, me, h, c).
Symbol Definition Numerical value
1 amu 1 atomic mass unit = 10−3/NA ≡ (1/12) of mass of = 1.660 540 2 × 10−23 kg
12
6C atom
ℏ ≡ h/2π = 1.054 571 635 × 10−34 J s
e ≡ Charge on electron in cgs-esu = 10ec = 4.803 206 799 × 10−10 sC
1 eV = (NAe/R) = 11 604.45 K = 10−2 (e/hc) = 8065.54 cm−1 = 8.065 54 kK
= (hc/e) = 1.239 842 447 × 10−6 m = 12 398.4 Å = 1239.84 nm
= {e} = 1.602 176 57 × 10−19 J
−14 4 4 −2
1 hartree ≡ e /a0 = 27.211 eV = 4π10
2
mee c h = 4.3558 × 10−18 J
1F ≡ NAe = 96 485.309 C mol−1
μB = 1 bohr magneton = 9.274 015 4 × 10−24 J T−1
eℏ 2me = eh 4πme = 9.274 015 4 × 10−21 erg G−1
2 −1
G0 ≡ 2e h = 1 quantum of electrical conductance = 7.748 091 696 × 10−5 S
= 1/von Klitzing/Landauer’s constant
Φ0 ≡ h/2e = 1 quantum of magnetic flux = 2.067 833 636 × 10−15 Wb
4πε0 = 107c−2 = 1.112 650 056 × 10−10 F m−1 (use this for SI unit conversions;
otherwise: s2 m−2)
μ0ε0 ≡ c−2 = 1.112 650 056 × 10−17 s2 m−2
−7
(μ0/ε0) 1/2
= μ0c = 4π10 c = Z0 (characteristic impedance = 376.730 313 461 Ω (for SI unit conversions; otherwise: m s−1)
of vacuum)
α ≡ Sommerfeld fine-structure constant = 7.297 353 080 × 10−3 (pure #) in esu
≡ e2/ℏc (using esu values for e,ℏ, c) = 1/137.035 989 5 (pure #) in esu
≡ e2/4πε0cℏ (using their SI values) = 1/137.035 989 5 (pure #) in SI
Table 1.10 Other conversion factors.
Unit Conversion Expression in SI base units Expression in other SI units
1 Å(ngstrom)a = 0.1 nm = 10−10 m(eters)

1 bohr = 0.052 917 725 nm = 0.529 177 25 Å = 5.291 772 5 × 10−11 m
1 Kb = Kayser = 1 wavenumber = 1 cm−1
−1 −1
1 Hz = (1/2π) cycles s = 1 (cycle) s
1 N = Newton 5
= 10 dyn = 1 kg ms−2 = 1 J m−1
2 −2
1 dyn = (1 abA) cm
1 dyn = (1 statC)2cm−2
1 Pa = Pascal c
= 0.007 500 616 Torr = 1 kg m−1 s−2 = 1 N m−2
1 (standard) atm = 101.325 kPa = 0.101 325 MPa = 760.000 0 Torr
1 P = Poised = cgs unit of viscosity = 1 g cm−1 s−1 = 0.1 Pa s
1 J = Joule = 107 erg = 1 kg m2 s−2 = 1 Ws = 1 N m
−1
1 erg = 1 statC cm 2
= 10−7 J = 1 sC sV
1 cal(orie) = 1 g-cal = 4.184 00 J
1 kcal = 1 kg-cal = 4.184 00 × 103 J
1 eV(olt) = 1.602 176 57 × 10−19 J = 1.602 176 57 × 10−12 erg
1 eV/molecule = 96.485 kJ/mol
1 hartree = 27.211 eV
1 C = Coulomb =1As =1CVs
1/2 3/2 −1
1 s(tat)C(coulomb) =1 g cm s(econd)
1 abC(coulomb) = 10 C
1 V = Volt = 1 kg m2 A−1 s−3 = 1 W A−1
−1
1 s(tat)V(olt) = 1 s(tat)C(oul) cm
1 abV(olt) = 108 V
1 Ohm = Ω = 1 V A−1 = 1 kg m2 A−2 s−3 = 1 W A−2
1 abΩ = 10−9 Ω
1 S = Siemens = 1 Ω−1 = 1 kg−1 m−2 A2 s3 = 1 A V−1
1 F = Farad = 1 C(oulomb)2 J(oule)−1 = 1 kg−1 m−2 A2 s4 = 1 C V−1
−2 −2
1 H = Henry 9
= 10 emu of inductance = 1 kg m A 2
s = 1 Wb A−1 = 1 V s A−1
1 W = Watte = 1 J(oule) s−1 = 1 A V s−1 = 1 C V s−2
−3
1 W(att) = 1 kg m s 2
= 1 J s−1 = 1 A V
1 Wb = Weber = 1 kg m2 A−1 s−2 =1Vs
1 T = Tesla 4
= 10 G(auss) = 1 kg A−1 s−2 = 1 Wb m−2 = 1 V s m−2
1 Oe = 1 g1/2 cm−1/2 s(econd)−1
−3
1 Oe cm 2
= 1 erg = 10−7 J
1 au time = 2 419 × 10 − 17 s = 2ε20 h3 πme e4
1 au electric field = electric field on electron 1 bohr radius from
proton = ea0− 2 = 1.7 × 107 sV cm−1 = 5.142 ×
1011 V m−1
1 au magnetic field = (wave or Gaussian convention) = aℏe − 1 a0− 2
= 1 716 × 103 T
1 au magnetic field = (Lorentz convention) = 2.5 × 105 T
f
1L = 1 monolayer
1 Da = Dalton = 1 atomic mass unit = mass, in g, of 6.022 ×
1023 hydrogen atoms
Unit Conversion Expression in SI base units Expression in other SI units
1 dirac = 1 word/h (after the taciturn Paul A.M. Dirac)

g
1 helen = beauty that can launch 1000 ships (after
Helen of Troy)
a
Anders Jonas Ångström (1814–1874).
b
Heinrich Gustav Johannes Kayser (1853–1940).
c
Blaise Pascal (1623–1682).
d
Jean Léonard Marie Poiseuille (1799–1869).
e
James Watt (1736–1819).
f
Irving Langmuir (1881–1957).
g
Helen of Sparta and Troy, daughter of Zeus and Leda; mythical (c. 1250 BC).
Table 1.11 Definitions of the electric field E, the (di)electric polarization P, the electric displacement D, the magnetic field H, the magnetization
M, the magnetic induction or flux density B, statement of the Maxwell equations, and of the Lorentz force equation in various systems of
units; rat. = rationalized (no 4π), unrat. = the explicit factor 4π is used in the definition of dielectric polarization and magnetization;
c = speed of light (using SI values for e, me, h, c) [1.29].
System Constitutive equations Maxwell equations Lorentz force Units
cgs-esu (unrat.) D = E + 4πP ∇ D = 4πρ ∇ × B = 4πJ + ∂D/∂t E+v×B E sV cm−1

P sC cm−2
D sC cm−2
H = c2B − 4πM ∇ B = 0 ∇ × D + ∂B/∂t = 0 H sA cm−1
M sA cm−1
B statT
cgs-emu (unrat.) D = c−2E + 4πP ∇ D = 4πρ ∇ × B = 4πJ + ∂D/∂t E+v×B E abV cm−1
P abC cm−2
H = B − 4πM ∇ B = 0 ∇ × D + ∂B/∂t = 0 D abC cm−2
H Oe
P = χ emuE MG
B = μemuH BG
M = χ emuH
Gaussian (cgs, D = E + 4πP ∇ D = 4πρ ∇ × B = 4πc−1J + c−1∂D/∂t E + c−1v × B E sV cm−1
unrat.) P sC cm−2
D sC cm−2
H = B − 4πM ∇ B = 0 ∇ × D + c−1∂B/∂t = 0 H Oe
MG
BG
Heaviside-Lorentz D = E+P ∇ D = ρ ∇ × B = c−1J + c−1∂D/∂t E + c−1v × B E sV cm−1
(cgs, rat.) P sC cm−2
D sC cm−2
H = B−M ∇ B = 0 ∇ × D + c−1∂B/∂t = 0 H Oe
MG
BG
Atomic units D = E + 4πP ∇ D = 4πρ ∇ × B = α(4πJ + ∂D/∂t) E+v×B E e b−2
(unrat.) (Hartree; P e b−2
Gauss convention) D e b−2
H = B − 4πM ∇ B = 0 ∇ D + α∂B/∂t = 0 H e b−2
M e b−2
B e b−2
(Continued)
System Constitutive equations Maxwell equations Lorentz force Units
Atomic units D = E + 4πP ∇ D = 4πρ ∇ × B = 4πJ + ∂D/∂t E+v×B E e b−2

(unrat.) (Hartree; P e b−2
Lorentz D e b−2
convention) H = B − 4πM ∇ B = 0 ∇ D + ∂B/∂t = 0 H e b−2
M e b−2
B e b−2
SI and SI (rat.) D = ε 0E + P ∇ D = ρ ∇ × B = J + ∂D/∂t E+v×B E V m−1
P C m−2
D C m−2
H = μ0− 1 B − M ∇ B = 0 ∇ D + ∂B/∂t = 0 H A m−1
M A m−1
BT
For Hartree atomic units of magnetism, two conventions exist: (i) the “Gauss” or wave convention, which requires that E and H have the same
magnitude for electromagnetic waves in vacuo; (ii) the Lorentz convention, which derives the magnetic field from the Lorentz force equation;
the ratio between these two sets of units is the Sommerfeld fine-structure constant α = 1/137.035 989 5.
Table 1.12 Conversion factors (using SI values for e, me, ℏ, and c).
Symbol Name SI esu (➔SI) emu (➔SI) au (➔SI)
L Length (do not confuse m cm cm b ≡ a0

this with inductance L) 10−2 10−2 5.292 × 10−11
= 107 ℏ ec 2 me− 1
m Mass kg g g electron mass ≡ me
10−3 10−3 ≡9.109 × 10−31
t Time s s s ℏ (hartree)
2.419 × 10−17
= 2ε20 h3 πme e4
v Speed m s−1 cm s−1 cm s−1 e2/ℏ
10−2 10−2 2.1877 × 106
= e2/2ε0h
V Volume (do not confuse m3 cm3 cm3 b3
this with V = Volt) 10−6 10−6 1.482 × 10−31
= a30
F Force N(ewton) dyn dyn hartree b−1
10−5 10−5 8.238 × 10−8
= mee4/a0(4πε0ℏ)2
W Work, energy J(oule) erg erg hartree
10−7 10−7 4.359 × 10−18
= e2/4πε0a0
= me e4 4ε20 h2
(The hartree is twice the ionization energy of the hydrogen atom)
A Action (do not confuse Js erg s erg s ℏ = Planck constant/2π
this with A = Ampère) 10−7 10−7 1.054 × 10−34
= h/2π
q Electric charge C(oulomb) s(tat)C(oulomb) abC Electron charge ≡ e
3.336 × 10−10 10 1.602 × 10−19
= 10−1c−1 ≡e
ρ Electric charge density C m−3 sC cm−3 abC cm−3 e b−3
3.336 × 10−4 10−5 1.081 × 1012
= 105c−1 = ea0− 3
mel Electrical dipole moment Cm sC cm abC cm electron bohr
3.334 × 10−8 0.1 8.478 × 10−30
= 10c−1 = ea0
(NB: 1 Debye = 3.336 × 10−30 C m = 4.803 sC cm = 2.541 e b = 4.803 e Å)

Qel Electrical quadrapole C m2 sC cm2 abC cm2 au
moment 3.336 × 10−3 4.487 × 10−40
10−14 = = ea20
10−3
= 10−5c−1
I Electric current A(mpère) statC s−1 abA = Biot e/‟au time”
3.336 × 10−10 10 6.624 × 10−3
= 10−1c−1 = e3/4πε0ℏa0
J Electric current density A m−2 statC s−1 cm−2 abA cm−2 e b−2(“au time”)−1
(volume) 3.336 × 10−6 103 2.365 × 1018
= 103c−1 = 1 28 × 10 − 26 π7 m3e c8 e9 h − 7
E Electric field V m−1 statV cm−1 abV cm−1 e b−2
2.998 × 104 1 × 10−6 5.142 × 1011
= 10−4c = e 4πε0 a0− 2
P (Di)electric polarization C m−2 statC cm−2 abC cm−2 e b−2
3.336 × 10−6 10−3 5.142 × 1011
= 103c−1 = ea0− 2
D Electric displacement C m−2 sC cm−2 abC cm−2 e b−2
dielectric induction 2.653 × 10−7 10−3 5.142 × 1011
= 103/4πc = ea0− 2
ε Dielectric constant pure # pure # pure # pure #
V Electric potential (do not V(olt) statV = sC cm−1 abV e b−1
confuse this with 2.998 × 102 10−8 27.211 39
V = volume) = 10−6c = e/4πε0a0
α Linear electric m3 cm3 cm3 b3 (Gauss convention)
polarizability 1.257 × 10−5 1.257 × 10−5 1.862 × 10−30
= 4π10−6 = 4π10−6 = 4πa30
SI : C m2 V−1 [SI / au (Gauss convention)
SI = ε0 = 1.649 × 10−41
8.854 × 10−12] = 4πε0 a30
= e2 a20 hartree
β First-order m4 V−1 cm5 abC−1 cm5 abC−1 au (Gauss convention)
nonlinear electric 4.192 × 10−10 2.998 × 104 3.622 × 10−42
hyperpolarizability = 4π10−2c−1 = 4π = 16π2 ε0 a50 e − 1
SI : C m3 V−2 au (Gauss convention)
[SI /SI = ε0 = 3.206 × 10−53
8.854 × 10−12] = e3 a30 hartree2
= 16π2 e20 a50 e − 1
γ Second-order SI: m5 V−2 cm7 sC−2 cm7 abC−2 au (Gauss convention)
nonlinear electric 1.398 × 10−14 1.256 × 10−5 7.042 × 10−54
hyperpolarizability = 4π102c−2 = 4π106 = 256π3 e20 a70 e − 2
SI : C m4 V−3 [SI / au (Gauss convention)
SI = ε0 = 6.235 × 10−65
8.854 × 10−12] = e4 a40 hartree3
= 256π3 e30 a70 e − 2
χ (1) First-order linear SI: pure # esu: pure # emu: pure # pure #
electrical susceptibility
SI : F m−1
[SI /SI = ε0 =
8.854 × 10−12]
χ (2) Second-order nonlinear SI: m V−1 sC sV−2 abC ab V−2 e(e b−1)−2
electrical susceptibility 4.192 × 10−4 5.171 × 10−30 2.444 × 10−11
= 4π104c−1 = 4π1012c−5 = 16π2 e20 a20 e − 1
SI’: C V−2
[SI /SI = ε0 =
8.854 × 10−12]
(Continued)
χ (3) Third-order nonlinear SI: m2 V−2 cm sC sV−3 cm abC abV−3 e b(e b−1)−3
electrical susceptibility 1.398 × 10−8 8.99 × 1022 4.208 × 10−34
= 4π108c−2 = 106c2 = 64π3 e30 a40 e − 2
SI : C m V−3
[SI /SI = ε0 =
8.854 × 10−12]
R Electrical resistance Ω s cm−1 abΩ au
1.113 × 1012 10−9 4.878 × 1014
= 105c−2 = e2a0 = h−1
G Electrical conductance S = mho cm s−1 abS au
8.988 × 1011 109 2.050 × 10−15
= 10−5c2 = e − 2 ha0− 1
ρ Electrical resistivity Ωm s abΩ cm Quantum of resistivity
(volume) 8.985 × 109 10−11 2.5813 × 104
= 10−7c2 = he−2
σ Electrical conductivity S m−1 s−1 abΩ−1 cm−1 Quantum of conductance
(volume) 1.113 × 10−10 10−7 3.874 × 10−5
= 107c−2 = e2h−1
C Electrical capacitance F(arad) statF = cm abF b
(do not confuse this with 1.113 × 10−12 109 5.29 × 10−11
C = Coulomb) = 105c−2 = a0
L Electrical inductance H(enry) statH = cm−1 s−2 abH b−1(au time)−2
1.113 × 10−8 10−9 3.229 × 1043
= 109c−2 = 10 − 7 π4 ε0− 4 m3e e10 c2 h − 8
m Magnetic dipole moment A m2 = J T−1 statA cm2 abA cm2 au (Gauss convention)
(loop; do not confuse this 3.34 × 10−14 = erg G−1 1.354 × 10−25
with m = mass) = 10−5c−1 10−3 = αeℏme− 1
au (Lorentz convention)
1.855 × 10−23
= eℏme− 1
j Magnetic dipole moment Wb m statT cm3 emu au (Lorentz convention)
(if B = μ0H + J, where =Vsm 3.77 × 1011 1.26 × 10−9 1.855 × 10−23
J = j × volume) = J m A−1 = 12π1010 = 4π10−10 = eℏ/me
μB Bohr magneton J T−1 erg stat T−1 erg G−1 au (Gauss convention)
10−3 10−3 6.769 × 10−26
= αeℏ/2me
9.274 × 10−24
= eℏ/2me
Φ Magnetic flux Wb = V s statT cm2 M(a)x(well) au (Gauss convention)
= J A−1 2.998 10−8 4.803 × 10−18
= 10−8c = 10−8 = αℏe−1 = ec × 10−7
6.583 × 10−16
=ℏe−1
B Magnetic T(esla) statT Gauss = abT au (Gauss convention)
induction = magnetic =Wb m−2 2.998 × 106 = Mx cm−2 1.716 × 103
flux density = magnetic = J A−1 m−2 = 10−2c 10−4 = αℏe − 1 a0− 2
field = V s m−2 au (Lorentz convention)
2.351 × 105
= ℏe − 1 a0− 2
H Magnetic field A m−1 statA cm∗−1 Oe = abA cm−1 au (Gauss convention)
strength = magnetizing 2.652 × 10−10 79.577 1.716 × 103 =
force (do not confuse this = 10−1/4πc ∗ = 103/4π = αℏe − 1 a0− 2
with H = Henry) au (Lorentz convention)
2.351 × 105
= ℏe − 1 a0− 2
M Volume magnetization A m−1 esu cm−3 emu cm−3 au (Gauss convention)

(moment/volume) 3.334 × 10−8 103 1.716 × 103
= 10 c−1 = aℏe − 1 a0− 2 au (Lorentz convention)
2.351 × 105
= ℏe − 1 a0− 2
U Magnetic potential A = A-turn esu Gb = Gilberta au (Gauss convention)
difference 2.654 × 10−10 0.7958 1.169 × 10−21
magnetomotive force = 1/4πc = 10/4π = αe
1.602 × 10−19
=e
J, I Magnetic polarization T = Wb m−2 esu cm−3 emu cm−3 au (Gauss convention)
intensity of 3.767 × 107 =erg/(Gg) 1.716 × 103
magnetization = 4πc10−2 1.257 × 10−3 = aℏe − 1 a0− 2
(if B = μ0H + J) =4π10−4 au (Lorentz convention)
2.351 × 105
= ℏe − 1 a0− 2
χ, κ (Volume) magnetic pure # pure # pure # au (Gauss convention)
susceptibility χ ≡ M/H➔ ➔12.57 ➔12.57 9.17 × 10−2
iff B = μ0(H + M) = 4π = 4π = α4π
➔12.57
= 4π
χ ≡M/H➔ SI :H m−1 1.579 × 10−5 au (Gauss convention)
iff B = μ0H + M = (4π)210−7 1.15 × 10−7
= α(4π)210−7
1.579 × 10−5
= (4π)210−7
χ ρ, κ ρ Mass magnetic m3 kg−1 cm3 g−1 au (Gauss convention)
susceptibility 1.257 × 10−2 ➔0.5638
χ ρ ≡ χ/density = 4π10−3 = α4πme a0− 3
iff B = μ0(H + M) au (Lorentz convention)
➔77.24
= 4πme a0− 3
iff B = μ0H + M SI ’ : H m2 kg−1 cm3 g−1 au (Gauss convention)
1.579 × 10−8 7.085 × 10−10
= (4π)210−10 = α 4π 2 10 − 7 me a0− 3
9.707 × 10−8
= 4π 2 10 − 7 me a0− 3
χ mol, κmol Molar magnetic m3 mol−1 cm3 mol−1 emu mol−1
susceptibility 10−6 1.257 × 10−5
iff B = μ0(H + M) = 4π10−6
iff B = μ0H + M SI :H m2 mol−1 emu mol−1
1.579 × 10−11
= (4π)210−13
μ Magnetic permeability H(enry) pure # au (Gauss convention)
μ ≡ B/H m−1 = Wb A−1 1.257 × 10−6 ➔1
m−1 = N A−2 = 4π10−7 au (Lorentz convention)
➔1
W Magnetic energy density J m−3 erg cm−3 hartree b−3
SI: W ≡ (1/2μ0)B2; cgs: ➔0.1 3.402 × 1014
W ≡ (1/8π)B2
For brevity a0 = Bohr radius = 5.292 × 10−11 m = 4πε0ℏ2m−1e−2. SI = Système International d’Unités = rationalized MKS = MKSC = MKSA = Giorgi
system; SI = small variation on SI used by some magneticians. “Rationalization” implies putting factors of 4π into the Maxwell equations and
removing them from the constitutive equations. Any quantity given in unrationalized cgs-esu (“esu”), unrationalized cgs-emu (“emu”), or unrationalized
au units is converted into SI units by multiplying the quantity by whatever follows the arrow “➔.” The au system used here is the “Hartree system”
(not the Rydberg system, nor the Planck system, nor the astronomical unit system). For the Hartree au of magnetism, two conventions exist: (i) the “Gauss”
or “wave” convention (inspired by cgs) requires that E and H in au have the same magnitude for electromagnetic waves in vacuo; (ii) the Lorentz
convention, which derives the magnetic field from the Lorentz force equation; the ratio between these units is the Sommerfeld fine-structure constant
α = 1/137.035 989 5.
a
William Gilbert (1544–1603).
Source: Jackson [1.29].
1.2 Force One: Gravitation
The gravitational force is the weakest force in nature, but it binds together the most massive bodies in the universe. The force
is in N(ewtons) in the SI system, and in dynes in the cgs system (see Table 1.2). This force can be rewritten in terms of a
vector gravitational field Φ1(r2) experienced by particle 2 at position r2, due to the existence of a particle 1 of mass m1 at
r1, and mediated by a continuous flow of virtual gravitons emanating from particle 1:
−3
Φ1 r 2 = Gm1 r 12 r 12 121
where r12 = r2 − r1. (By definition, a process is virtual when it involves a temporary violation of energy conservation.)
This gravitational field can be integrated once to yield the scalar gravitational potential energy U1:
U 1 = Gm1 r 1− 1 122
where the field is the negative gradient of the potential U1 evaluated at any “field point” r, e.g. r = r2 (except at the singular
position r = r1):
Φ1 = − ∇U 1 = − er ∂ ∂r U 1 123
where er is the unit vector in the radial direction. This potential energy is measured in joules, J (1 J ≡ 1 N m)10 in the SI
system, or in erg (1 erg ≡ 1 dyn cm) in the cgs system. We can also define the gravitational potential energy U12 as the
potential energy of the two-body system:
−1
U 12 = Gm1 M 2 r 12 124
What is mass? Six answers can be given:
1) as a proportionality constant between force and acceleration;

2) “gravitational mass” (Eq. (1.1.1));
3) “inertial mass”;
4) Einstein11 found an interdependence between mass m and energy E (1905):
E = mc2 125
within his special theory of relativity [1.8] (Section 1.11), which explained why the speed of light c through vacuum is con-
stant, validating the 1887 Michelson12–Morley13 experiment [1.9], which found a zero seasonal dependence of c and elimi-
nated the need for a “luminiferous ether” for the propagation of light. Equation (1.2.5) allows for the interconversion of mass
and energy: this is at the core of nuclear physics and stellar synthesis.
(5) Einstein’s general theory of relativity [1.10] allows for a curvature of the space-time continuum, which can lead to a
geometrical understanding of mass (Wheeler’s14 geometrodynamics [1.11]).
(6) Quantum mass: the rest masses of elementary particles cannot yet be predicted, but a Higgs15 boson has finally been
found in 2013: it may usher in a future theory to explain their masses.
Experimental searches are still continuing for free quarks and gluons.
Given the dearth of new results from high-energy scattering studies, high-energy physics has also turned to the cosmos for
clues: the current ΛCDM (lambda-cold dark matter) model of “big bang cosmology” estimates that of all matter in the uni-
verse: (i) 23% is dark matter (Zwicky16 proposed dark matter in 1933 to account for the gravitational stability of visible
galaxies); (ii) 73% is dark energy; (iii) 5% is “normal” (visible) matter.
10 James Prescott Joule (1818–1889).

11 Albert Einstein (1879–1955).
12 Albert Abraham Michelson (1852–1931).
13 Edward Williams Morley (1838–1923).
14 John Archibald Wheeler (1911–2008).
15 Peter Higgs (1929–).
16 Fritz Zwicky (1898–1974).
A discussion of the second force (electrical AKA electromagnetic) is given in Section 1.9 after some necessary
mathematical concepts and tricks are reviewed.
Problem 1.2.1 Given the mass of the Earth Me = 5.977 × 1024 kg and its mean radius Re = 6371 km, verify that the
acceleration due to mean gravity at sea level at the Equator is
g = GM e Re− 2 = 9 780 m s − 2 126
1.3 Force Three: Weak Force
The classic example of the weak (or Fermi) force is β decay, in which a free neutron (0n1) decays within a half-life t1/2 of
10.2 minutes into a proton (1p1), an electron (e−), and an electron antineutrino νe :
1 1
0n 1p + e + v t1 2
= 10 2 m = 611 s 131
As explained in Chapter 6, a sample with N0 free neutrons at t = 0 will decay by first-order kinetics and will have only
N = N0 exp(−0.693 15t/t1/2) neutrons at time t. The half-life t1/2 in Eq. (1.3.1) is defined as the time needed for half of the
sample (here, of free neutrons) to have undergone the stated reaction; a second, longer, measure of “endurance” is the
mean lifetime τ which is defined by
τ = t1 2
ln e 2 = t 1 2
0 693 15 = 1 44t 1 2
132
3
The weak force is 10 times weaker than the electromagnetic force (Table 1.1). The particles carrying this interaction, the
W and Z vector bosons, are surprisingly massive (see Tables 1.2 and 1.3).
The positron(β+) is the antiparticle of the electron (e− or β−): same mass, same spin, but opposite charge. Antiparticles,
first discussed in the 1930s, seemed to be like members of an alternate universe (antiprotons, etc.) which may be symmet-
rical to the particle universe. However, when a positron (often emitted in nuclear decay) encounters an electron, it anni-
hilates very quickly to produce two photons of energy hν = 0.511 MeV each (pair elimination):
β + + β− 2hν 133
This reaction can also be run in reverse (pair production) either in air or also when a photon interacts with a nucleus:
2 hν β + + β− 134
There are also short-lived and negatively charged antiprotons. In the 1930s, it was presumed that there are equal numbers
of particles and antiparticles in the universe (which would annihilate each other upon mutual contact as in Eq. (1.3.3)). At
present, the guesses are shifting to smaller amounts of antimatter, but nobody really knows.
The Fermi force has a very narrow range (10−18 m). Many nuclei can undergo spontaneous β decay. Neutrinos (a name
given by Fermi) carry little mass, occur with great abundance in the universe, but are very difficult to detect (they often pass
through the mass of the Earth without deflection or detection). Huge tanks of liquid chlorinated hydrocarbons in deep
mines have been successfully tested for neutrino-induced formation of a few atoms of radioactive argon.
Many artificial radioisotopes undergo β decay. For instance, in the upper atmosphere, 6C14 is generated by cosmic rays
(neutron bombardment of 7N14) to yield a constant fraction of radioactive carbon in living matter by photosynthetic absorp-
tion of 6C14O2(1.3 × 10−12); it decays by β decay, with a half-life of 5730 years, into stable 7N14: this is the basis of Libby’s
archeological carbon-14 dating method [1.12]:
7N
14
+ 0 n1 from cosic ray shower 6C
14∗
β decay 7N
14 +
+ β − + νe 135
1.4 Force Four: Strong Force
Chemists are often content to ignore quarks and stay with the evidence accumulated by 1930 that electrically neutral atoms
of atomic number Z are made of Z protons (1p1), N neutrons (0n1), and Z electrons (e− or β−) (Table 1.13) and that these
subatomic particles are characterized by relative mass M, charge Q, spin (S for electron, I for proton and neutron), and half-
lives τ. Furthermore Q, S, and I are also “quantum numbers” (more about this later).
Table 1.13 Simplified table of elementary particles used in low-level chemistry courses: me = 9.109 389 7 × 10−31 kg is the electron
rest mass; ε = − 1.602 176 57 × 10−19 C is the charge on the electron.
Name Symbol Half-life t1/2 (s) Mass M (me) Charge Q (|ε|) Spin S or I
Electron e− or β− ∞ 1 −1 1/2
Proton 1p
1
∞ 1838 +1 1/2
1
Neutron 0n 611 1839 0 1/2
Physicists probed much further: between 1900 and 1960, a zoo of 100-odd stable and/or unstable elementary particles was
discovered; the shortest-lived among them were called “resonances” (Table 1.2). Quarks (Tables 1.2 and 1.3) were proposed
in 1964 by Zweig17 and Gell-Mann18 to establish order in this zoo. Within the nucleus, the inter-nucleon “strong” force was
traditionally thought of as being mediated by pions (themselves combinations of two quarks). The nuclear “shell model”
assigns quantum numbers to the protons and neutrons that have merged to form a certain nucleon. Certain “magic values”
of these nuclear quantum numbers explain why certain nuclei are more stable (have longer lives) than others.
Efforts to unify all four forces of Table 1.1 into a single grand unified theory have failed. All of eighteenth and nine-
teenth century mathematical physics was based on continua, on the solution of second-order partial differential equations
(PDEs), and on microscopic extensions of macroscopic Newtonian ideas of distance-dependent potentials. As we shall see,
classical mechanics, electrodynamics, and quantum mechanics (in its wave mechanical formulation) all have potential
energy functions U(r) which are some function of the inter-particle distance r. This works well if the particles themselves
are much smaller than the distances that typically separate them, and when experiments can test the distance dependence of
the potentials directly.
What are we to do when the range of the strong forces are so short (Table 1.1), of the order of magnitude of the presumed
particle sizes?
Much progress was made nevertheless. In 1960, electrical and weak forces were merged by Glashow19 into the electro-
weak theory. Evolving in the 1960s and 1970s from the quark hypothesis, Glashow, Weinberg,20 and Salam21 explained
nucleons and other particles (hadrons, baryons, and mesons) as unions of either three or two “quarks” each, with a new set
of ad hoc “quantum numbers” (charge Q, spin [S or I], parity [P], isospin [T], z-component of isospin [Tz], baryon number
[Ba], strangeness [St], charm [Ch], beauty or bottomness [By], and truth or topness [Tr]) [1.3] (Tables 1.2 and 1.3) which fit
within a finite special unitary group SU(3): all this was called quantum chromodynamics (QCD). An internal relation-
ship between these many seemingly “ad hoc” quantum numbers is the amended Gell–Mann–Nishijima22 relation:
Q = T z + Ba + St + Ch + By + Tr 2 141
Adding the electroweak theory to QCD and explaining gravity by positing a Higgs field bathing the whole universe, the
overall theory was named the Standard Model (outlined in Special Topic ST1.11): it unites three of the four fundamental
forces (strong, weak, and electromagnetic) into a single theory, but has no force field, and addresses gravitation only by
positing that moving particles acquire their masses by moving within this Higgs field. The discovery of the mediating Higgs
boson in 2012 (with a surprisingly large mass) validated the concept of a universal and pervasive Higgs field: how exactly
does it “create” masses? Remember that a universal luminiferous ether was discarded from electromagnetic theory more
than a century ago!
Sideline 1.5 We should always remember Newton’s stern warning: “Physica, cave metaphysicam” (=physicists,
beware of metaphysics) and Ockham’s23 “razor”: “entia non sunt multiplicanda praeter necessitatem” (=fundamen-
tal assumed quantities should not be multiplied beyond necessity).
17 George Zweig (1937–).

18 Murray Gell-Mann (1929–2019).
19 Sheldon Glashow (1932–).
20 Steven Weinberg (1933–).
21 Mohammed Abdus Salam (1926–1996).
22 Kazuhiko Nishijima (1926–2009).
23 William of Ockham (c.1285–1348).
Already, the existence of spin angular momentum forces us to consider quantization without potentials (see Chapter 2).
Perturbation expansions become funny, since the interaction is no longer smaller than a presumed over-riding field. When
the particles are too close, or the potential wells are too deep, then the old tricks do not seem to apply. What to do? Instead of
the four dimensions used in special relativity (x, y, z, and ct: see Section 1.11 below), string theory posits 17 dimensions, but
has produced no experimentally verifiable prediction to date: is it useful? Is it necessary?
The seemingly ex post facto arguments and numerous new quantum numbers in the Standard Model are reminiscent of
the situation in 1869, when chemical trends were used by Mendeleyeff to construct his epochal Periodic Table of chemical
elements: the mathematical explanation and vindication for the Periodic Table came with the Schrödinger24 equation
of 1926.
Sideline 1.6 Besides his chemical discovery, Mendeleyeff had helped his government in the design of weaponry.
Mendeleyeff divorced his wife in 1882 and married a student: by the rules of the Russian Orthodox Church, he
was a bigamist, and according to an Edict of the Russian Czar, only members of the Church in good standing could
teach in Russian Universities. When apprised of the dilemma, Czar Alexander III25 thought for a moment, then said:
“Prof. Mendeleyeff may have two wives, but I only have one Mendeleyeff”: Mendeleyeff kept his job!
Sideline 1.7 When the Nobel Prizes were initiated in 1901, Mendeleyeff was still alive: he was the obvious candidate
for the Chemistry prize: it did not happen because a jealous Svante Arrhenius26 was lusting for his own prize (which
he did get in 1916). Instead of Mendeleyeff, some nonentities were awarded the first few Chemistry Prizes. Many
other deserving scientists were neglected: the names of Gilbert Newton Lewis27 and Henry Eyring28 come to mind.
Therefore, this book will not highlight the Nobel prizes, which have honored many worthy recipients, but have
bypassed so many others.
Present guesses about the origin of the Universe suggest that matter and energy were all concentrated in a subnanoscopic
“singularity” at “t = 0,” the beginning of the Universe (about 14 billion years ago, see Problem 1.13.1). Within a very short
time (Planck time), the Big Bang explosion started the Universe, the four fundamental forces differentiated, and galaxies and
the oldest stars and planets were born.
Tables 1.2 and 1.3 list the presently known fundamental particles (along with unobserved quarks and three kinds of
neutrinos and antineutrinos), the elementary particles, and the observed particles (photon, vector bosons, Higgs boson,
graviton) and unobserved particles (gluons, some bosons) that mediate the interactions (strong, electromagnetic, weak, and
gravitational) between them. Here the term “fundamental” is used for the presumed building blocks, while the term “ele-
mentary” is reserved for the experimentally observed smallest constituents of matter. Recent work suggests that the three
kinds of neutrinos shown in Table 1.2 have small but differing rest masses (of the order of 10−3me) and that neutrino oscilla-
tions (interconversions) between their three types are possible.
The half-lives t1/2 or lifetimes τ can measured directly when τ ≥ 1.0 × 10−12 s or so. Shorter lifetimes (t < 1.0 × 10−12 s)
are inferred from measuring the “natural” or Breit29–Wigner30 or Lorentzian31 linewidth ΔE of their energy E (see Special
Topic ST1.1) and then using the Heisenberg32 uncertainty principle (discussed in Chapter 2).
Searches for individual quarks using high-energy accelerators have failed, up to rest-mass energies in vast excess of the
masses of the stable known leptons and hadrons. Searches for quarks in minerals and sea water, potentially left over when
hadrons and leptons first formed, and focused on their putative fractional electrical charge, have also failed. Therefore, an
explanation of “quark confinement” has emerged: quarks are confined by twos and threes in a very deep potential well
inside baryons and mesons (Figure 1.1), and are held together by forces so strong, that only maybe future high-energy accel-
erator experiments may (if ever) detect an individual quark. The sum of the estimated sum of the probable rest masses of one
u, one u, and one d quark, namely 4.6 + 4.6 + 16.0 = ~25.2me is far short of the rest mass of the proton (1836me); the remain-
ing 1811me are tentatively ascribed to the Einstein mass energy (Eq. (1.2.5)) of the gluon interchanging between quarks.
24 Erwin Rudolf Josef Alexander Schrödinger (1887–1961).

25 Alexander III Alexandrovich Romanov, Czar of All the Russias (1845–1894).
26 Svante August Arrhenius (1859–1927).
27 Gilbert Newton Lewis (1875–1946).
28 Henry Eyring (1901–1981).
29 Gregory Breit (1899–1981).
30 Eugene Paul Wigner = Jenö Pál Wigner (1902–1995).
31 Hendrik Antoon Lorentz (1853–1928).
32 Werner Heisenberg (1901–1976).
Nuclei of atoms can be thought of as super-dense combinations of “nucleons”: Z protons

(1p1) and N neutrons (0n1). Thus, nuclei have a formal nucleon number A given by A ≡ Z
–u + N “nucleons,” the experimental nuclear mass is M(Z,A). For any chemical element, e.g.
u
“Et,” the isotope with Z protons and A protons + neutrons is designated as “ZEtA” or “Et
A” or “Et-A.” Table X1 (please refer www.wiley/go/metzger/physchemtoolbox2) lists most
known nuclei.
d
The nuclear densities (1014–1015 g cm−3 = 1017–1018 kg m−3) are so great that the nucleons
are in intimate contact with each other, held together by the strong force, is attractive
Proton between 2.0 and 0.7 fm, but repulsive below 0.7 fm. It was thought in the 1930s that this
internucleon force is mediated by pions; at present, gluons (in a residual nuclear strong
Figure 1.1 This crude model force) must also be considered. Some distance-dependent potentials (e.g. Yukawa33) have
tries to show the confinement
of three quarks (“up” (u),
been partially successful.
“conjugate up” (u), and “down” Nuclei are less massive than the sum of the masses of Z free protons and N-free neutrons:
(d), with electrical charges this mass defect, or nuclear binding energy ΔE, or mass loss, increases with atomic number,
+2/3, +2/3, and −1/3) inside a up to Fe. ΔE in atomic mass units (the mass of one 6C12 nucleus is 12.000 atomic mass units)
proton. The springs depict the
mutual interactions, meditated
is given by
by virtual gluons, which are
(somehow) limited by the ΔE Z, A − M Z, A − 1 007 825Z + 1 008 665 A − Z 142
inter-quark potential to remain
within the inside of the proton. This binding energy is colossal, when compared to chemical bond energies, is released
in stellar nucleosynthesis, and can be partially released in fission and fusion reactions
(A-bombs, H-bombs, nuclear power plants: see Section 9.2). The quotient ΔE/A rises from
He to Fe, allowing for exergonic nucleosynthesis in stars. However, ΔE/A declines beyond Fe
(Figure 1.2): this explains why successive gravitational collapses of dying stars form first He
stars, then C stars, then Ne stars, then finally Fe stars. When all nuclear fuel is depleted in an
Fe star, an ultimate gravitational collapse into black holes must occur, if the star mass
exceeds eight solar masses, i.e. >1.6 × 1031 kg; otherwise, the star will decay into a
white dwarf.
9
O16 U235
Average binding energy per nucleon (MeV)
Fe56
8 C12 U238
He4
7
6
Li7
5 Li6
3 H3
He3
2
2
1 H
1
0 H
0 30 60 90 120 150 180 210 240 270
Number of nucleons in nucleus
Figure 1.2 Average binding energy per nucleon ΔE/A for stable nuclei, as a function of mass number A. Source: Nuclear Binding energy
curve [1.13].
33 Hideki Ogawa Yukawa (1907–1981).

Some nuclei are stable: for low-Z elements, N ≈ Z for stable nuclei (e.g. 6C12, 7N14, or 8O16); for high-Z elements, N ≈ 2Z is a
predictor of stability (infinite half-life). As first suggested by Soddy34 in 1913, several nuclei can share the same atomic num-
ber Z: they are isotopes. Some isotopes are stable. A large majority of the isotopes are radioactive and unstable (particularly
for Z > 92) and decay into nuclear “daughters” with a bewildering range of half-lives t1/2. Some high-Z radioactive isotopes
occur in nature: they are the decay products of other isotopes formed eons ago when the Earth was formed and decay pro-
gressively into lighter daughters, ultimately ending the chain of nuclear decays into an isotope of lead (Pb) (Section 9.2).
Much experimental efforts on making high-Z elements are driven by curiosity and by so far empty promises of possible
“islands of stability” around Z ≈ 120. Most other radioactive nuclei are formed by irradiating stable nuclei with energetic
nuclear particles; natural or artificial radioactive nuclei (N, Z, A) can exhibit several decay modes into new nuclei (N , Z ,
A ) by
i) α-decay (N = N − 4, Z = Z − 2; A = A − 4; with emission of a 2He4 nucleus, i.e. helium-4 dictation (2He4)2+, which is
dominant for elements of atomic number greater than Pb);
ii) β-decay or electron emission (N = N − 1; Z = Z + 1; A = A; this involves the weak force and the extra emission of an
electron antineutrino);
iii) positron or β+ decay (N = N + 1; Z = Z − 1; A = A, emission of a positron and an electron neutrino; this also involves
the weak force);
iv) γ decay: no changes in N or Z;
v) electron capture (N = N + 1; Z = Z − 1; A = A, emission of electron; this also involves the weak force);
vi) internal conversion, from a metastable nucleus to a more stable nucleus with no particle emission.
Several models were adopted to explain the structure of stable and radioactive nuclei. The liquid drop model assumes
that protons and neutrons coalesce to form a liquid drop of high density (spherical, or prolate spheroidal, or oblate sphe-
roidal). Weizsäcker’s35 semiempirical mass formula accounts fairly well for the masses M(Z,A) (in atomic mass units) for
stable nuclei:
M Z, A = 1 007 825Z + 1 008 665 A − Z − 0 016 91A + 0 019 11A2 3

+ 0 000 763Z 2 A − 1 3
143
+ 0 101 75 Z − A 2 2 A − 1 + − 1, 0, or + 1 0 012A − 1 2
However, assuming that all nuclei are drops of nuclear matter would predict all
nuclei to be spherical (many are not) and cannot account for the relative stability of
certain nuclei called “islands of (relative) nuclear stability” (Z and/or N = 2, 8, 20,
5 6 7
28, 50, 82, 126, 184). A much better nuclear shell model was developed by Göp- 3Li 3Li 3Li
pert-Mayer36 and Jensen37 (Special Topic ST1.2). β out,
+
d out p out EC
Very useful is a wall chart of all nuclides developed by the Knolls Atomic Power
Laboratory of the General Electric Company in the 1950s and updated continuously 6 7 8
4Be 4Be 4Be
since then (Table X1 [please refer www.wiley/go/metzger/physchemtoolbox2])
Original
[1.14]. Figure 1.3 shows schematically how this chart of the nuclides is arranged. n out nucleus n in
Problem 1.4.1 Table X1 (please refer www.wiley/go/metzger/physchemtool- 7 8 9
5B 5B 5B
box2) shows that the mass of the radioactive isotope 5B13 is 13.017 780 amu. It
emits an electron β− and an electron antineutrino to yield the stable isotope β– out p in d in
13
6C of mass 13.003 354 8. Neglecting any energy carried away by the electron
antineutrino, compute the energy emission. (Answer: 13.436 MeV)
Figure 1.3 Diagrammatical
representation of how an original
Problem 1.4.2 The free neutron undergoes β decay to a proton, an electron, and nucleus (here 4Be7) can be transformed
an electron antineutrino, with a half-life of 13.6 minutes. (a) But when you add a into its neighbors by absorption or
proton to the neutron to form a deuteron (D), there is no β decay. Why? (b) In emission of nuclear particles
(d = deuteron = 1H2 = positively charged
contrast, tritium (T: 1 proton + 2 neutrons) does undergo β decay (half-life hydrogen-2). Full details are given in
12.32 years) to 1He3. Why? Table X1. EC = Electron capture.
34 Frederick Soddy (1877–1956).

35 Carl Friedrich Freiherr von Weizsäcker (1912–2007).
36 Maria Göppert-Mayer (1906–1972).
37 Johannes Hans Daniel Jensen (1907–1973).
Problem 1.4.3 Black hole (Figure 1.4). A photon of total energy E = hν = mc2 becomes una-
ble to escape the gravitational potential of a massive spherical black hole (a term popularized
hv = m02 by Wheeler) of density ρ = 1014 g cm−3 (the density of a light atomic nucleus) and radius R.
E = mc2 = GmM R = Gmρ 4 3 πR3 R 144

Find the radius R of the black hole and its mass M. Then compare the mass of the black hole
M to the mass of our Sun, 1.985 × 1030 kg. This resembles the Schwarzschild38 radius R that
R occurs in the spherically symmetric solution to Einstein’s field equations for general relativity.
However, the Schwarzschild radius is twice smaller. Read up on Hawking’s39 explanation of
ρ = 1014 g cm–3
even horizons and how a black hole will keep absorbing everything until it either decreases its
density or explodes.
Figure 1.4 A photon of Problem 1.4.4 Assume that the charge on the proton becomes +2|e| instead of +|e|, and that
rest energy E = hν = m0c2
cannot escape the everything else stays the same. What would be the consequences for chemistry?
gravitational pull of a cold
black hole of radius R and Problem 1.4.5 The negative muon, or mu meson, μ− is 207 times heavier than the electron
density 1014 g cm−3. and is a natural product of cosmic rays (which first produce pions that decay into muons), or it
can be made in particle accelerators. It has a lifetime of 2.2 μs (decaying into an electron and
two neutrinos). It can replace the electron in mu-mesic atoms and molecules. Would it produce
a drastic modification in atomic and molecular structure?
Problem 1.4.6 Positrons (e+ or β+) are “antielectrons” which can form bound states with electrons (e− or β−, “nega-
trons” if you like) before they decay. “Positronium” is a hydrogen-like structure, where the positron replaces the positively
charged proton, or hydrogen nucleus. Would this be like a hydrogen atom?
Whenever stable nuclei exist, stable chemical elements are possible. The PERIODIC TABLE OF THE CHEMICAL
ELEMENTS (Table 1.14) was first organized by Mendeleyeff in 1869 [1.15] well before quantum mechanics and the mod-
ern theory of atomic structure, by using group analogies in chemical and physical properties.
Sideline 1.8 In the 1780s, Lavoisier40 first pinpointed the “irreducibility” of chemical elements (like hydrogen and
oxygen) into simpler elements and their combination in chemical compounds (like water). In the early 1800s, Dalton41
revived the ancient idea of indivisible “fundamental” atoms proposed by Leucippus42 and his pupil Democritus.43 Dal-
ton also demonstrated two laws (of definite and multiple proportions): as a result, relative empirical formulas and sep-
arate and sometimes contrasting tables of relative atomic weights were established for a growing list of chemical
compounds. For several decades, the molecular structure of water was erroneously assumed to be “HO.” Avogadro’s
1811 principle that at constant pressure and temperature equal volumes of gases contained an equal number of mole-
cules was ignored until Cannizzaro’s 1858 work,44 circulated at the Karlsruhe conference of 1860, convinced the Ger-
man chemists to finally take Avogadro’s principle seriously: Shazaam: the molecular formula for water became H2O, all
relative scales rolled into one, and Mendeleyeff could then build his magnificent periodic table!
Problem 1.4.7 We now have 118 chemical elements, but the elements beyond U (element 92) are produced in nuclear
reactors (e.g. Pu) or by collisions of lighter elements with high-energy ions (e.g. Og was made by colliding Cf with calcium
ions; only three or four Og atoms were produced!). By its placement, Og is a “noble gas” in Group 18 (albeit a very reactive
one because its nucleus soon decays by emitting an α ray). Does this close down the search for stable transuranium elements?
Problem 1.4.8 Why is iron Fe? Why is mercury Hg? Why is tungsten W?
Problem 1.4.9 Which two elements were named after living scientists?
38 Karl Schwarzschild (1873–1916).

39 Stephen William Hawking (1942–2018).
40 Antoine-Laurent de Lavoisier (1743–1794).
41 John Dalton (1766–1844).
42 Leucippus of Elea (early 5th c. BC).
43 Democritus of Abdera (c. 460–370 BC).
44 Stanislao Cannizzaro (1826–1910).
Table 1.14 The periodic table of the known chemical elements.
Group 1 Group 2 Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12 Group 13 Group 14 Group 15 Group 16 Group 17 Group 18
/1A/ /2A/ /3B/ /4B/ /5B/ /6B/ /7B/ /8B/ /8B/ /8B/ /1B/ /2B/ /3A/ /4A/ /5A/ /6A/ /7A/ /8A/
Hydrogen Helium
1 2
H He
1.0079 4.0026
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon

3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.0122 10.811 12.011 14.0067 15.9994 18.9984 20.1797
Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon

11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
22.9898 24.3050 26.9815 28.0855 30.9738 32.066 35.4527 39.948
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.0983 40.078 44.955912 47.867 50.9415 51.9961 54.938045 55.845 58.933195 58.6934 63.546 65.38 69.723 72.64 74.92160 78.96 79.904 83.798
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Sliver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.4678 87.62 88.90585 91.224 92.90638 95.96 (98) 101.07 102.90550 106.42 107.8682 112.411 114.818 118.710 121.760 127.60 126.90447 131.293
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9054511 137.327 138.90547 178.49 180.94788 183.84 186.207 190.23 192.217 195.084 196.966569 200.59 204.3833 207.2 208.98040 (209) (210) (222)
Francium Radium Actinium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Röntgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac‡ Rf Db Sg Bh Hs Mt Ds Rg Cn Nh Fl Mc Lv Ts Og
(223) (226) (227) (267) (268) (271) (272) (270) (276) (281) (280) (285) (284) (289) (288) (293) (294) (294)
Cerium Praseodymium Neodymium Protoactinium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.116 140.90765 144.242 (145) 150.36 151.964 157.25 158.92535 162.500 164.93032 167.259 168.93421 173.054 174.9668
Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium
‡90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.03806 231.03588 238.02891 (237) (244) (243) (247) (247) (251) (252) (257) (258) (259) (262)
The 18 groups (Group n) are the modern ones; the older grouping is given inside slashes, e.g. /7B/.
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Girls are good as they can be,
But boys are best you must agree.
I guess I’ve tol’ you all I know

From where names come to where they go;
But ’member now ’ist what I sed,
My name is Bub instead o’ Ned.
THE VEGETABLE MAN

By Leonard G. Nattkemper
A Chinaman comes to our house each day

Wif horses that’s colored both red an’ gray,
An’ wagon ’ist full of things to eat—
An’ up I climbs on his big high seat.
This Chinaman’s name I cannot tell—

But “veg’table man” will do as well;
For corn an’ beans and cabbage, too,
He grows in the fields for me an’ you.
An’ w’en it’s time to drive to town

He brings his wagon ’ist loaded down
With veg’t’ble things an’ peaches too—
He’ll peel you one if I ask him to.
Gee, but I love this Chinaman;

He stops an’ plays, an’ one day ran
Aroun’ his wagon clear out of sight—
But I found him there an’ held on tight.
Then up he lifts me way up high,

An’ laughs again wif his funny eye—
I forgot to tell that he can see
’Ist half so well as you an’ me.
’Cause one day w’en he’s ’ist a boy

An’ playin’ wif a home-made toy,
It flew aroun’ an’ hit his face,
An’ left that funny open place.
But I don’t care if he is queer,

He sees enough to know I’m here,
An’ finds the time to stop an’ play
W’en I am lonesome through the day.
But ma an’ dad are not so kind

As veg’t’ble man whose eye is blind.
I guess I love them all I can,
But most I love my Chinaman.
IMMIGRATION
By Wallace Irwin
Ezekiel, the Puritan,

Thus lifts his protestation:
“By ginger, I’m American,
And don’t like immigration.
Naow I jest guess I got here fust
And know what I’m abaout,
When I declar’ we’ll all go bust
Or keep them aliens out.”
Max Heidelburg, the German, says:

“Jah also. Right, mein frendt.
If ve dot foreign trash admit
Our woes will nefer endt.
I am Americans as you
Und villing to ge-shout
‘Hurray mit red und vite und plue,
Und kiip dose aliens oudt!’”
Ike Diamondstein, the Jew, exclaims:

“Ah, Izzy, ain’t dat grandt!
Ve Yangees haf such nople aims
Und vill togeder standt,
Ve’ve got der goods, ve’re nach’ralized—
Vat hinters us from shouten
‘Americavich is civilzized,
So keep dose aliens outen!’”
Pietro Garibaldi says:

“Here ever-r-ry man is king.
I catch-a da fun, I mak-a da mon,
I like-a da ever-r-yt’ing.
American he gent-a-man—
Watch-a da Dago shout,
‘Sell-a da fruit, shin-a da boot,
Keep-a da alien out!’”
The Irishman vociferates:

“Sure, Mike, it’s sahft as jelly.
I’ll take the shtick and crack the pates
Of ivery foreign Kelly.
If it’s the call o’ polyticks,
Then I’m the la’ad to shout,
‘Down wid th’ Da-agos an’ th’ Micks,
An’ keep th’ aliens out!’”
But covered with ancestral tan,

Beside his wigwam door,
The only real American
Counts idle talk a bore.
“Ugh! Pale-face man he mighty thief.
Much medicine talk about—
It heap too late for Injun chief
To keep-um alien out.”
PATHETIC SELECTIONS IN POETRY
PASSIN’ BY[11]
By Bombardier B. Bumpas
Well, I went an’ joined the army, an’ I done my little bit—
’Ere’s the bloke wot put my pot on; yes, I keeps ’im in my kit—
No, ’e ain’t no proper soft-nose; just the end off on the sly;
’E’s the only one wot got me—but I’ve ’eard ’em passin’ by,
God A’mighty! Yes, I’ve ’eard ’em passin’ by.
Passin’ by; passin’ by; with a little whistlin’ sigh,

“Nearly got you that time, Sonny, just a little bit too high,”
Or a crack like, “Jack, look out there: Keep yer ’ead down, mind yer
eye!”
But they’re gone an’ far behind yer ’fore you’ll ’ear ’em passin’ by.
Yes, I lay from Toosday mornin’ till the Wensday afternoon;

’En the Black Watch took their trenches ’en it woke me from a
swoon.
I was flamin’, nearly mad wi’ thirst an’ pain, an’ fit to cry,
But I cheered ’em as they trampled on me carcus, passin’ by.
God A’mighty! Yes, I cheered ’em as I ’eard ’em passin’ by.
Passin’ by; passin’ by; trippin’, failin’, gettin’ nigh.

Gettin’ nearer to the trenches, ’en you ’eard a Tommy cry:
“Don’t forget the Belgian wimmen, nor the little bairns forbye.”
God! I wouldn’t be a German when them men was passin’ by.
Then they gathered us together an’ they sorted out the worst—
Wot they called the “stretcher cases”—and they ’tended to us first,
They was overworked an’ crowded, an’ the Doc ’ud give a sigh—
“Hopeless, that case”—“that one, also”—speakin’ softly, passin’ by.
God! They watched ’im, silent, suff’rin’, watchin’, hopin’—passin’ by.
Passin’ by; passin’ by; curt command an’ stifled sigh,
For it ain’t no place for drama, an’ a man ’as got ter die;
’En I thought I ’eard a whimper an’ a little soft reply—
“Greater love than this hath no man”—some one speakin’ passin’ by.
So they ships me off to “Blighty,” ’en they sticks me in a ward,

I was short a leg an’ peeper, but they treats me like a lord.
I’d allus bin a lonely bloke, an’ so I used ter lie
An’ watch the fren’s of other men continual passin’ by,
Sisters, children, wives, an’ mothers, everlastin’ passin’ by.
Passin’ by; passin’ by; with a smile or with a sigh;

With their cigarettes an’ matches, flowers or shirt or pipe or tie;
An’ one ’ud sometimes talk an’ speak—I used ter wonder why—
Cos I ain’t no blame Adonis, not ter notice, passin’ by.
I’m thinkin’ if the angels ’ave a Union Jack around,

An’ sticks it somewhere prominent when Gabriel starts to sound,
The people round that flag will be ’most half the hosts on high—
The men who’ve passed, or waits to pass, or now are passin’ by,
Big ’earted men an’ wimmen, white an’ black, a-passin’ by.
Passin’ by; passin’ by; just to keep that flag on high,

An’ all that flag ’as stood for in the days that’s now gone by;
An’ when they pass before, I’m sure ’E’ll listen to their cry,
An’ ’E’ll treat ’em very gentle, an’ forgive ’em, passin’ by.
JEANIE MORRISON
By William Motherwell
I’ve wandered east, I’ve wandered west,

Through mony a weary way;
But never, never can forget
The luve o’ life’s young day!
The fire that’s blawn on Beltanes e’en
May weel be black ’gin Yule;
But blacker fa’ awaits the heart
Where first fond luve grows cule.
O dear, dear Jeanie Morrison,

The thochts o’ bygane years
Still fling their shadows ower my path,
And blind my een wi’ tears:
They blind my een wi’ saut, saut tears,
And sair and sick I pine,
As memory idly summons up
The blithe blinks o’ langsyne.
’Twas then we luvit ilk ither weel,

’Twas then we twa did part;
Sweet time,—sad time! twa bairns at scule,
Twa bairns, and but ae heart!
’Twas then we sat on ae laigh bink,
To leir ilk ither lear;
And tones and looks and smiles were shed,
Remembered evermair.
I wonder, Jeanie, aften yet,

When sitting on that bink,
Cheek touchin’ cheek, loof locked in loof,
What our wee heads could think.
When baith bent doun ower ae braid page,
Wi’ ae buik on our knee,
Thy lips were on thy lesson, but
My lesson was in thee.
O, mind ye how we hung our heads,

How cheeks brent red wi’ shame,
Whene’er the scule-weans, laughin’, said
We cleeked thegither hame?
And mind ye o’ the Saturdays,
(The scule then skail’t at noon,)
When we ran off the speel the braes,—
The broomy braes o’ June?
My head rins round and round about,—
My heart flows like a sea,
As ane by ane the thochts rush back
O’ scule-time and o’ thee.
O mornin’ life! O mornin’ luve!
O lichtsome days and lang,
When hinnied hopes around our hearts
Like summer blossoms sprang!
O, mind ye, luve, how aft we left

The deavin’ dinsome toun,
To wander by the green burnside,
And hear its waters croon?
The simmer leaves hung ower our heads,
The flowers burst round our feet,
And in the gloamin’ o’ the wood
The throssil whusslit sweet;
The throssil whusslit in the wood,

The burn sang to the trees,—
And we, with Nature’s heart in tune,
Concerted harmonies;
And on the knowe abune the burn
For hours thegither sat
In the silentness o’ joy, till baith
Wi’ very gladness grat.
Ay, ay, dear Jeanie Morrison,

Tears trinkled doun your cheek
Like dew-beads on a rose, yet nane
Had ony power to speak!
That was a time, a blessed time,
When hearts were fresh and young,
When freely gushed all feelings forth,
Unsyllabled,—unsung!
I marvel, Jeanie Morrison,

Gin I hae bin to thee
As closely twined wi’ earliest thocts
As ye hae been to me?
O, tell me gin their music fills
Thine ear as it does mine!
O, say gin e’er your heart grows grit
Wi’ dreamings o’ langsyne?
I’ve wandered east, I’ve wandered west,

I’ve borne a weary lot;
But in my wanderings, far or near,
Ye never were forgot.
The fount that first burst frae this heart
Still travels on its way;
And channels deeper, as it rins,
The luv o’ life’s young day.
O dear, dear Jeanie Morrison,

Since we were sindered young
I’ve never seen your face, nor heard
The music o’ your tongue;
But I could hug all wretchedness,
And happy could I dee,
Did I but ken your heart still dreamed
O’ bygone days and me!
CUDDLE DOON
By Alexander Anderson
The bairnies cuddle doon at nicht

Wi’ muckle faught an’ din;
“Oh, try and sleep, ye waukrief rogues,
Your faither’s comin’ in.”
They never heed a word I speak;
I try to gie a froon,
But aye I hap them up an’ cry,
“Oh, bairnies, cuddle doon.”
Wee Jamie wi’ the curly heid—
He aye sleeps next the wa’—
Bangs up an’ cries, “I want a piece;”
The rascal starts them a’.
I rin an’ fetch them pieces, drinks,
They stop awee the soun’,
Then draw the blankets up an’ cry,
“Noo, weanies, cuddle doon.”
But ere five minutes gang, wee Rab

Cries out, frae neath the claes,
“Mither, mak’ Tam gie ower at once,
He’s kittlin’ wi’ his taes.”
The mischief’s in that Tam for tricks,
He’d bother half the toon,
But aye I hap them up and cry,
At length they hear their faither’s fit,

An’ as he steeks the door,
They turn their faces to the wa’,
While Tam pretends to snore.
“Hae a’ the weans been gude?” he asks,
As he pits off his shoon;
“The bairnies, John, are in their beds,
An’ lang since cuddled doon.”
And just afore we bed oorsels,

We look at our wee lambs;
Tam has his airm roun’ wee Rab’s neck,
And Rab his airm round Tam’s.
I lift wee Jamie up the bed,
An’ as I straik each croon,
I whisper, till my heart fills up,
The bairnies cuddle doon at nicht

Wi’ mirth that’s dear to me;
But soon the big warl’s cark an’ care
Will quaten doon their glee.
Yet, come what will to ilka ane,
May He who rules aboon
Aye whisper, though their pows be beld
THE PATRIOT
By Robert Browning
(An Old Story)
It was roses, roses, all the way,

With myrtle mixed in my path like mad:
The house-roofs seemed to heave and sway,
The church-spires flamed, such flags they had,
A year ago on this very day.
The air broke into a mist with bells,

The old walls rocked with the crowd and cries.
Had I said, “Good folk, mere noise repels—
But give me your sun from yonder skies!”
They had answered “And afterward, what else?”
Alack, it was I who leaped at the sun

To give it my loving friends to keep!
Naught man could do, have I left undone:
And you see my harvest, what I reap
This very day, now a year is run.
There’s nobody on the house-tops now

Just a palsied few at the windows set;
For the best of the sight is, all allow,
At the Shambles’ Gate—or, better yet,
By the very scaffold’s foot, I trow.
I go in the rain, and, more than needs,

A rope cuts both my wrists behind;
And I think, by the feel, my forehead bleeds,
For they fling, whoever has a mind,
Stones at me for my year’s misdeeds.
Thus I entered, and thus I go!

In triumphs, people have dropped down dead.
“Paid by the world, what dost thou owe
Me?” God might question; now instead,
’Tis God shall repay: I am safer so.
ANNABEL LEE
By Edgar Allan Poe
It was many and many a year ago,

In a kingdom by the sea,
That a maiden there lived whom you may know
By the name of Annabel Lee;
And this maiden she lived with no other thought
Than to love and be loved by me.
I was a child and she was a child,

In this kingdom by the sea,
But we loved with a love that was more than love,
I and my Annabel Lee;
With a love that the winged seraphs of heaven
Coveted her and me.
And this was the reason that, long ago,

In this kingdom by the sea,
A wind blew out of a cloud, chilling
My beautiful Annabel Lee,
So that her highborn kinsmen came
And bore her away from me,
To shut her up in a sepulchre
In this kingdom by the sea.
The angels, not half so happy in heaven,
Went envying her and me;
Yes! that was the reason (as all men know,
In this kingdom by the sea)
That the wind came out of the cloud by night,
Chilling and killing my Annabel Lee.
But our love it was stronger by far than the love

Of those who were older than we,
Of many far wiser than we;
And neither the angels in heaven above,
Nor the demons down under the sea,
Can ever dissever my soul from the soul
Of the beautiful Annabel Lee:
For the moon never beams, without bringing me dreams

Of the beautiful Annabel Lee;
And the stars never rise, but I feel the bright eyes
Of the beautiful Annabel Lee;
And so, all the night-tide, I lie by the side
Of my darling—my darling—my life and my bride,
In her sepulchre there by the sea,
In her tomb by the sounding sea.
THE LOVER OF ANNABEL LEE

By Edwin D. Casterline
Often I think of the beautiful soul,

The soul of Annabel Lee,
And the man who loved, in the years gone by,
The soul of Annabel Lee—
His beautiful bride, who sleeps by his side,
By the shores of the sounding sea.
They say he was mad, but the world was mad,

More mad and more wrong than he,
For the soul was true that loved the soul
Of the wondrous Annabel Lee,
And the touch of that love was the love that made
The soul of her lover free.
In the days gone by, in the wreck of things,

From the wave of Life’s wide sea,
They were carried beyond by their kinsmen high,
He and his Annabel Lee;
Her heart was pure, too pure for the world
That chills the heart of the free—
And his was a life that chilled with the life
That passed from Annabel Lee.
But the angels are good; in heaven above

They gather the wrecks of the sea,
They gather the gold from the wrecks of love,
And the soul in its purity free—
So this is what they’ve done with the love
Of Poe and his Annabel Lee.
I’ve stood in the room where they lived and loved,

And my soul touched the Life to be,
And I felt the spell of the hidden light
That lived in Annabel Lee;
And I felt the hand of the man she loved,
(That she loved far better than we,)
And down in my soul the double soul
Awoke the God in me.
So down in my dreams I follow the beams

Of Poe and his Annabel Lee,
And deep in the night I see the pure light
That flashes and quivers to me.
Away in the years where the Future stands,
In the world that is to be,
I know that my hands will clasp the hands
Of Poe and his Annabel Lee.
THE BURIED HEART
By Dennar Stewart
“I sleep, but my heart waketh.”
Tread lightly, love, when over my head,

Beneath the daisies lying,
And tenderly press the grassy bed
Where the fallen rose lies dying.
Dreamless I sleep in the quiet ground,

Save when, your foot-fall hearing,
My heart awakes to the old-loved sound
And beats to the step that’s nearing.
Bright shone the moon, last eve, when you came—

Still, dust for dust hath feeling—
The willow-roots whispered low the name
Of him who weeps while kneeling.
The lily-cup holds the falling tears,

The tears you shed above me;
And I know through all these silent years
There’s some one still to love me.
Oh, softly sigh; for I hear the sound

And grieve me o’er your sorrow;
But leave a kiss in the myrtle mound—
I’ll give it back to-morrow.
Whisper me, love, as in moments fled,

While I dream your hand mine taketh;
For the stone speaks false that says, “She’s dead;”
I sleep, but my heart awaketh.
BREAK! BREAK! BREAK!

By Alfred Tennyson
Break, break, break,

On thy cold gray stones, O Sea!
And I would that my tongue could utter
The thoughts that arise in me.
O, well for the fisherman’s boy,

That he shouts with his sister at play!
O, well for the sailor-lad,
That he sings in his boat on the bay!
And the stately ships go on

To their haven under the hill;
But, O, for the touch of a vanish’d hand,
And the sound of a voice that is still!
Break, break, break,

At the foot of thy crags, O Sea!
But the tender grace of a day that is dead
Will never come back to me.
BESIDE THE DEAD

By Ina Coolbrith
(One of the finest sonnets in the English language)
It must be sweet, O thou, my dead, to lie

With hands that folded are from every task;
Sealed with the seal of the great mystery,
The lips that nothing answer, nothing ask.
The life-long struggle ended; ended quite
The weariness of patience, and of pain,
And the eyes closed to open not again
On desolate dawn or dreariness of night.
It must be sweet to slumber and forget;
To have the poor tired heart so still at last:
Done with all yearning, done with all regret,
Doubt, fear, hope, sorrow, all forever past:
Past all the hours, or slow of wing or fleet—
It must be sweet, it must be very sweet!
—From “Songs of the Golden Gate,” copyright by Houghton,

Mifflin & Co., and used by kind permission of author and publisher.
ROCKING THE BABY

By Madge Morris Wagner
I hear her rocking the baby—

Her room is just next to mine—
And I fancy I feel the dimpled arms
That round her neck entwine,
As she rocks, and rocks the baby,
In the room just next to mine.
I hear her rocking the baby
Each day when the twilight comes,
And I know there’s a world of blessing and love
In the “baby bye” she hums.
I see the restless fingers
Playing with “mamma’s rings,”
And the sweet little smiling, pouting mouth,
That to hers in kissing clings,
As she rocks and sings to the baby,
And dreams as she rocks and sings.
I hear her rocking the baby,

Slower and slower now,
And I know she is leaving her good-night kiss
On its eyes, and cheek, and brow.
From her rocking, rocking, rocking,
I wonder would she start,
Could she know, through the wall between us,
She is rocking on a heart,
While my empty arms are aching
For a form they may not press,
And my emptier heart is breaking
In its desolate loneliness?
I list to the rocking, rocking,
In the room just next to mine,
And breathe a prayer in silence,
At a mother’s broken shrine,
For the woman who rocks the baby
In the room just next to mine.
—Copyright by Harr Wagner Co., San Francisco, and used by kind

permission of author and publisher.
PUT FLOWERS ON MY GRAVE

By Madge Morris Wagner
When dead, no imposing funeral rite,

Nor line of praise I crave;
But drop your tears upon my face—
Put flowers on my grave.
Close not in narrow wall the place

In which my heart finds rest,
Nor mark with tow’ring monument
The sod above my breast.
Nor carve on gleaming, marble slab

A burning thought or deed.
Or word of love, or praise, or blame,
For stranger eyes to read.
But deep, deep in your heart of hearts,

A tender mem’ry save;
Upon my dead face drop your tears—
Put flowers on my grave.
—Copyright by Harr Wagner Co., San Francisco, and used by kind
permission of author and publisher.
THE OLD FAMILIAR FACES

By Charles Lamb
I have had playmates, I have had companions,

In my days of childhood, in my joyful school days;
All, all are gone, the old familiar faces.
I have been laughing, I have been carousing,

Drinking late, sitting late, with my bosom cronies;
I loved a love once, fairest among women;

Closed are her doors on me, I must not see her—
I have a friend, a kinder friend has no man;

Like an ingrate, I left my friend abruptly;
Left him, to muse on the old familiar faces.
Ghost-like I paced round the haunts of my childhood,

Earth seemed a desert I was bound to traverse,
Seeking to find the old familiar faces.
Friend of my bosom, thou more than a brother,

Why wert thou not born in my father’s dwelling?
So might we talk of the old familiar faces—
How some they have died, and some they have left me,
And some are taken from me; all are departed;
I FEEL I’M GROWING AULD, GUDE-WIFE

By James Linen
I feel I’m growing auld, gude-wife—
I feel I’m growing auld;
My steps are frail, my een are bleared,
My pow is unco bauld.
I’ve seen the snaws o’ fourscore years
O’er hill and meadow fa’,
And hinnie! were it no’ for you,
I’d gladly slip awa’.

Frae youth to age I’ve keepit warm
The love that ne’er turned cauld.
I canna bear the dreary thocht
That we maun sindered be;
There’s naething binds my poor auld heart
To earth, gude-wife, but thee.

Life seems to me a wintry waste,
The very sun feels cauld.
Of worldly frien’s ye’ve been to me,
Amang them a’ the best;
Now, I’ll lay down my weary head,
Gude-wife, and be at rest.
DA THIEF[12]
By T. A. Daly
Eef poor man goes

An’ steals a rose
Een Juna-time—
Wan leetla rose—
You gon’ su’pose
Dat dat’s a crime?
Eh! w’at? Den taka look at me,
For here bayfore your eyes you see
Wan thief, dat ees so glad an’ proud
He gona brag of eet out loud!
So moocha good I do, an’ feel,
From dat wan leetle rose I steal,
Dat eef I gon’ to jail to-day
Dey no could tak’ my joy away.
So, leesen! here ees how eet come:
Las’ night w’en I am walkin’ home
From work een hotta ceety street
Ees sudden com’ a smal so sweet

Eet maka heaven een my nose—
I look an’ dere I see da rose!
Not wan, but manny, fine an’ tall,
Dat peep at me above da wall.
So, then, I close my eyes an’ find
Anudder peecture een my mind;
I see a house dat’s small an’ hot
Where many pretta theengs ees not,
Where leetla woman, good an’ true,
Ees work so hard da whole day through,
She’s too wore out, w’en com’s da night,
For smile an’ mak’ da housa bright.
But presto! now I’m home, an’ she

Ees seetin’ on da step weeth me.
Bambino, sleepin’ on her breast,
Ees nevva know more sweeta rest,
An’ nevva was sooch glad su’prise
Like now ees shina from her eyes;
An’ all baycause to-night she wear
Wan leetla rose stuck een her hair.
She ees so please’! Eet mak’ me feel
I shoulda sooner learned to steal!

The Physical Chemists Toolbox 2Nd Edition Robert M Metzger Full Chapter

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The Physical Chemist’s Toolbox 2nd

Edition Robert M. Metzger

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Library of Congress Cataloging-in-Publication Data Applied for:

Cover Design: Wiley

Set in 9.5/12.5pt STIXTwoText by Straive, Pondicherry, India

1 Fundamental Particles, Fundamental Forces, and Mathematical Tools 1

2 Quantum Mechanics 147

2.3.3 Gamow Calculation 161

4 Statistical Mechanics 327

4.5.5 Electronic Excitation 341

5 Kinetics, Equilibria, and Electrochemistry 363

6.10 Reciprocal Lattice 456

7 Solid State Physics 469

8 Electrical Circuits, Amplifiers, and Computers 519

8.13 Historical Introduction to Computers 557

9 Sources, Sensors, and Detection Methods 577

9.29 Geiger–Müller Counter 624

11 Inorganic Chemistry and Nanomaterials 749

11.17.31 From Group 17: Fluorine 814

12 Organic and Polymer Chemistry and Catalysis 833

12.14.20 BAc2 (Basic Conditions, Acyl Transfer, Bimolecular) 877

Preface and Philosophy

“Felix qui potuit rerum cognoscere causas”

1) summarize common bases of mathematics, physics, chemistry, and materials science,

About the Companion Website

This textbook is supported by a website which contains a variety of supplementary resources:

Online you will find:

Fundamental Particles, Fundamental Forces, and Mathematical Tools

“It is difficult to make predictions, especially about the future”

1 Dmitri Ivanovich Mendeleyeff (1834–1907).

The Physical Chemist’s Toolbox, Second Edition. Robert M. Metzger.

PART ONE: Fundamental Forces

1.1 Fundamental Forces, Elementary Particles, Nuclei, and Atoms

F 12 = − Gm1 M 2 r 12 r 312 111

Table 1.1 The fundamental forces.

Force Law Equation Mediating particle Relative magnitude Range

Gravitation Newton’s F 12 = − Gm1 M 2 r 12 r 312 Graviton 10−39 Infinite

3 Michael Faraday (1791–1867).

Electron neutrino νe ∞ 0 0 1/2 −1 0 0 0 0 0 0 0

Table 1.3 Standard model of elementary particles.

Three historical generations of fermions

m = 4.7 MeVc–2 m = 96 MeVc–2 m = 4.18 MeVc–2

m < 2.2eV c–2 m < 1..7MeV c–2 m = 80.39

Note that “gauge” is a misnomer for “phase.”

F 12 = q1 q2 r 12 4πε0 r 312 112

7 James Clerk Maxwell (1831–1879).

Table 1.4 Fundamental constants (gram-mole = molar mass in grams).

Name Symbol SI value

Gravitational constant G 6.673 84 × 10−11 m3 kg−1 s−2

Table 1.5 Other constants.

Name Symbol Equation SI value

Sommerfelda fine-structure constant α = e2/2ε0ch 1/137.035 999(=e2/ℏc in esu)

Some important constants are given in Tables 1.4 and 1.5.

9 James Augustine Aloysius Joyce (1882–1941).

Table 1.6 SI base unitsa.

Name Symbol Unit Abbreviation

deca da ×10+1 deci d ×10−1

Table 1.8 Atomic units (using SI values for e, me, h, c).

Quantity Description Symbol Size (in SI units)

Charge Charge of the electron e −1.602 176 57 × 10−19 A s

Table 1.8 (Continued)

Quantity Description Symbol Size (in SI units)