<p>Preface xv</p> <p>About the companion website xvii</p> <p><b>1 Introduction 1</b></p> <p>1.1 Atoms and molecules 1</p> <p>1.2 Phases 2</p> <p>1.3 Energy 3</p> <p>1.4 Chemical reactions 4</p> <p>1.5 Problem solving 5</p> <p>1.6 Some conventions 7</p> <p>Exercises 11</p> <p>Further reading 14</p> <p><b>2 Ideal gases 15</b></p> <p>2.1 Ideal gas equation of state 16</p> <p>2.2 Molecular degrees of freedom 18</p> <p>2.3 Translational energy: Distribution and relation to pressure 21</p> <p>2.4 Maxwell distribution of molecular speeds 23</p> <p>2.5 Principle of equipartition of energy 24</p> <p>2.6 Temperature and the zeroth law of thermodynamics 25</p> <p>2.7 Mixtures of gases 27</p> <p>2.8 Molecular collisions 27</p> <p>Exercises 29</p> <p>Further reading 30</p> <p><b>3 Non-ideal gases and intermolecular interactions 31</b></p> <p>3.1 Non-ideal behavior 31</p> <p>3.2 Interactions of matter with matter 32</p> <p>3.3 Intermolecular interactions 34</p> <p>3.4 Real gases 39</p> <p>3.5 Corresponding states 42</p> <p>3.6 Supercritical fluids 43</p> <p>Exercises 43</p> <p>Further reading 44</p> <p><b>4 Liquids, liquid crystals, and ionic liquids 45</b></p> <p>4.1 Liquid formation 45</p> <p>4.2 Properties of liquids 45</p> <p>4.3 Intermolecular interaction in liquids 47</p> <p>4.4 Structure of liquids 50</p> <p>4.5 Internal energy and equation of state of a rigid sphere liquid 52</p> <p>4.6 Concentration units 53</p> <p>4.7 Diffusion 55</p> <p>4.8 Viscosity 57</p> <p>4.9 Migration 59</p> <p>4.10 Interface formation 60</p> <p>4.11 Liquid crystals 62</p> <p>4.12 Ionic liquids 64</p> <p>Exercises 66</p> <p>Further reading 67</p> <p><b>5 Solids, nanoparticles, and interfaces 68</b></p> <p>5.1 Solid formation 68</p> <p>5.2 Electronic structure of solids 70</p> <p>5.3 Geometrical structure of solids 72</p> <p>5.4 Interface formation 76</p> <p>5.5 Glass formation 78</p> <p>5.6 Clusters and nanoparticles 78</p> <p>5.7 The carbon family: Diamond, graphite, graphene, fullerenes, and carbon nanotubes 80</p> <p>5.8 Porous solids 83</p> <p>5.9 Polymers and macromolecules 84</p> <p>Exercises 86</p> <p>Endnotes 86</p> <p>Further reading 86</p> <p><b>6 Statistical mechanics 87</b></p> <p>6.1 The initial state of the universe 88</p> <p>6.2 Microstates and macrostates of molecules 89</p> <p>6.3 The connection of entropy to microstates 91</p> <p>6.4 The constant 𝛼: Introducing the partition function 93</p> <p>6.5 Using the partition function to derive thermodynamic functions 94</p> <p>6.6 Distribution functions for gases 96</p> <p>6.7 Quantum statistics for particle distributions 98</p> <p>6.8 The Maxwell–Boltzmann speed distribution 102</p> <p>6.9 Derivation of the ideal gas law 103</p> <p>6.10 Deriving the Sackur–Tetrode equation for entropy of a monatomic gas 104</p> <p>6.11 The partition function of a diatomic molecule 106</p> <p>6.12 Contributions of each degree of freedom to thermodynamic functions 106</p> <p>6.13 The total partition function and thermodynamic functions 111</p> <p>6.14 Polyatomic molecules 113</p> <p>Exercises 115</p> <p>Endnotes 116</p> <p>Further reading 116</p> <p><b>7 First law of thermodynamics 117</b></p> <p>7.1 Some definitions and fundamental concepts in thermodynamics 118</p> <p>7.2 Laws of thermodynamics 118</p> <p>7.3 Internal energy and the first law 119</p> <p>7.4 Work 121</p> <p>7.5 Intensive and extensive variables 123</p> <p>7.6 Heat 124</p> <p>7.7 Non-ideal behavior changes the work 125</p> <p>7.8 Heat capacity 126</p> <p>7.9 Temperature dependence of C<i><sub>p</sub> </i>127</p> <p>7.10 Internal energy change at constant volume 129</p> <p>7.11 Enthalpy 130</p> <p>7.12 Relationship between C<i><sub>V</sub></i> and C<i><sub>p</sub></i> and partial differentials 131</p> <p>7.13 Reversible adiabatic expansion/compression 133</p> <p>Exercises 136</p> <p>Endnotes 138</p> <p>Further reading 138</p> <p><b>8 Second law of thermodynamics 139</b></p> <p>8.1 The second law of thermodynamics 140</p> <p>8.2 Thermodynamics of a hurricane 141</p> <p>8.3 Heat engines, refrigeration, and heat pumps 145</p> <p>8.4 Definition of entropy 148</p> <p>8.5 Calculating changes in entropy 150</p> <p>8.6 Maxwell’s relations 152</p> <p>8.7 Calculating the natural direction of change 154</p> <p>Exercises 157</p> <p>Endnotes 159</p> <p>Further reading 159</p> <p><b>9 Third law of thermodynamics and temperature dependence of heat capacity, enthalpy and entropy 160</b></p> <p>9.1 When and why does a system change? 160</p> <p>9.2 Natural variables of internal energy 161</p> <p>9.3 Helmholtz and Gibbs energies 162</p> <p>9.4 Standard molar Gibbs energies 163</p> <p>9.5 Properties of the Gibbs energy 164</p> <p>9.6 The temperature dependence of <b>Δ</b><sub>r</sub><i>C<sub>p</sub></i> and <i>H</i> 168</p> <p>9.7 Third law of thermodynamics 170</p> <p>9.8 The unattainability of absolute zero 171</p> <p>9.9 Absolute entropies 172</p> <p>9.10 Entropy changes in chemical reactions 173</p> <p>9.11 Calculating <b>Δ</b><sub>r</sub><i>S</i><sup>◦</sup> at any temperature 175</p> <p>Exercises 177</p> <p>Further reading 180</p> <p><b>10 Thermochemistry: The role of heat in chemical and physical changes 181</b></p> <p>10.1 Stoichiometry and extent of reaction 181</p> <p>10.2 Standard enthalpy change 182</p> <p>10.3 Calorimetry 184</p> <p>10.4 Phase transitions 187</p> <p>10.5 Bond dissociation and atomization 190</p> <p>10.6 Solution 191</p> <p>10.7 Enthalpy of formation 192</p> <p>10.8 Hess’s law 192</p> <p>10.9 Reaction enthalpy from enthalpies of formation 193</p> <p>10.10 Calculating enthalpy of reaction from enthalpies of combustion 194</p> <p>10.11 The magnitude of reaction enthalpy 195</p> <p>Exercises 196</p> <p>Further reading 200</p> <p><b>11 Chemical equilibrium 201</b></p> <p>11.1 Chemical potential and Gibbs energy of a reaction mixture 201</p> <p>11.2 The Gibbs energy and equilibrium composition 202</p> <p>11.3 The response of equilibria to change 204</p> <p>11.4 Equilibrium constants and associated calculations 209</p> <p>11.5 Acid–base equilibria 212</p> <p>11.6 Dissolution and precipitation of salts 216</p> <p>11.7 Formation constants of complexes 219</p> <p>11.8 Thermodynamics of self-assembly 222</p> <p>Exercises 224</p> <p>Endnote 228</p> <p>Further reading 228</p> <p><b>12 Phase stability and phase transitions 229</b></p> <p>12.1 Phase diagrams and the relative stability of solids, liquids, and gases 229</p> <p>12.2 What determines relative phase stability? 232</p> <p>12.3 The <i>p–T</i> phase diagram 234</p> <p>12.4 The Gibbs phase rule 237</p> <p>12.5 Theoretical basis for the <i>p–T</i> phase diagram 238</p> <p>12.6 Clausius–Clapeyron equation 240</p> <p>12.7 Surface tension 242</p> <p>12.8 Nucleation 246</p> <p>12.9 Construction of a liquid–vapor phase diagram at constant pressure 250</p> <p>12.10 Polymers: Phase separation and the glass transition 252</p> <p>Exercises 254</p> <p>Endnotes 255</p> <p>Further reading 256</p> <p><b>13 Solutions and mixtures: Nonelectrolytes 257</b></p> <p>13.1 Ideal solution and the standard state 258</p> <p>13.2 Partial molar volume 258</p> <p>13.3 Partial molar Gibbs energy = chemical potential 259</p> <p>13.4 The chemical potential of a mixture and <b>Δ</b><sub>mix</sub>G 261</p> <p>13.5 Activity 263</p> <p>13.6 Measurement of activity 264</p> <p>13.7 Classes of solutions and their properties 269</p> <p>13.8 Colligative properties 273</p> <p>13.9 Solubility of polymers 277</p> <p>13.10 Supercritical CO<sub>2</sub> 279</p> <p>Exercises 281</p> <p>Endnote 282</p> <p>Further reading 282</p> <p><b>14 Solutions of electrolytes 283</b></p> <p>14.1 Why salts dissolve 283</p> <p>14.2 Ions in solution 284</p> <p>14.3 The thermodynamic properties of ions in solution 287</p> <p>14.4 The activity of ions in solution 289</p> <p>14.5 Debye–Huckel theory 290</p> <p>14.6 Use of activities in equilibrium calculations 292</p> <p>14.7 Charge transport 295</p> <p>Exercises 298</p> <p>Further reading 299</p> <p><b>15 Electrochemistry: The chemistry of free charge exchange 300</b></p> <p>15.1 Introduction to electrochemistry 301</p> <p>15.2 The electrochemical potential 306</p> <p>15.3 Electrochemical cells 310</p> <p>15.4 Potential difference of an electrochemical cell 312</p> <p>15.5 Surface charge and potential 318</p> <p>15.6 Relating work functions to the electrochemical series 319</p> <p>15.7 Applications of standard potentials 321</p> <p>15.8 Biological oxidation and proton-coupled electron transfer 326</p> <p>Exercises 329</p> <p>Endnotes 331</p> <p>Further reading 332</p> <p><b>16 Empirical chemical kinetics 333</b></p> <p>16.1 What is chemical kinetics? 333</p> <p>16.2 Rates of reaction and rate equations 335</p> <p>16.3 Elementary versus composite reactions 336</p> <p>16.4 Kinetics and thermodynamics 337</p> <p>16.5 Kinetics of specific orders 338</p> <p>16.6 Reaction rate determination 345</p> <p>16.7 Methods of determining reaction order 346</p> <p>16.8 Reversible reactions and the connection of rate constants to equilibrium constants 348</p> <p>16.9 Temperature dependence of rates and the rate constant 350</p> <p>16.10 Microscopic reversibility and detailed balance 353</p> <p>16.11 Rate-determining step (RDS) 354</p> <p>Exercises 355</p> <p>Endnotes 359</p> <p>Further reading 359</p> <p><b>17 Reaction dynamics I: Mechanisms and rates 360</b></p> <p>17.1 Linking empirical kinetics to reaction dynamics 360</p> <p>17.2 Hard-sphere collision theory 361</p> <p>17.3 Activation energy and the transition state 364</p> <p>17.4 Transition-state theory (TST) 366</p> <p>17.5 Composite reactions and mechanisms 368</p> <p>17.6 The rate of unimolecular reactions 372</p> <p>17.7 Desorption kinetics 374</p> <p>17.8 Langmuir (direct) adsorption 378</p> <p>17.9 Precursor-mediated adsorption 380</p> <p>17.10 Adsorption isotherms 381</p> <p>17.11 Surmounting activation barriers 382</p> <p>Exercises 386</p> <p>Endnotes 389</p> <p>Further reading 390</p> <p><b>18 Reaction dynamics II: Catalysis, photochemistry and charge transfer 391</b></p> <p>18.1 Catalysis 392</p> <p>18.2 Heterogeneous catalysis 393</p> <p>18.3 Acid–base catalysis 402</p> <p>18.4 Enzyme catalysis 403</p> <p>18.5 Chain reactions 407</p> <p>18.6 Explosions 410</p> <p>18.7 Photochemical reactions 411</p> <p>18.8 Charge transfer and electrochemical dynamics 415</p> <p>Exercises 428</p> <p>Endnotes 431</p> <p>Further reading 431</p> <p><b>19 Developing quantum mechanical intuition 433</b></p> <p>19.1 Classical electromagnetic waves 434</p> <p>19.2 Classical mechanics to quantum mechanics 443</p> <p>19.3 Necessity for an understanding of quantum mechanics 444</p> <p>19.4 Quantum nature of light 448</p> <p>19.5 Wave–particle duality 449</p> <p>19.6 The Bohr atom 453</p> <p>Exercises 458</p> <p>Endnotes 460</p> <p>Further reading 461</p> <p><b>20 The quantum mechanical description of nature 462</b></p> <p>20.1 What determines if a quantum description is necessary? 463</p> <p>20.2 The postulates of quantum mechanics 463</p> <p>20.3 Wavefunctions 464</p> <p>20.4 The Schrodinger equation 467</p> <p>20.5 Operators and eigenvalues 469</p> <p>20.6 Solving the Schr ¨ odinger equation 471</p> <p>20.7 Expectation values 475</p> <p>20.8 Orthonormality and superposition 477</p> <p>20.9 Dirac notation 480</p> <p>20.10 Developing quantum intuition 481</p> <p>Exercises 486</p> <p>Endnotes 488</p> <p>Further reading 488</p> <p><b>21 Model quantum systems 489</b></p> <p>21.1 Particle in a box 490</p> <p>21.2 Quantum tunneling 495</p> <p>21.3 Vibrational motion 497</p> <p>21.4 Angular momentum 500</p> <p>Exercises 511</p> <p>Endnotes 513</p> <p>Further reading 513</p> <p><b>22 Atomic structure 514</b></p> <p>22.1 The hydrogenl atom 515</p> <p>22.2 How do you make it better? the Dirac equation 518</p> <p>22.3 Atomic orbitals 520</p> <p>22.4 Many-electron atoms 524</p> <p>22.5 Ground and excited states of He 528</p> <p>22.6 Slater–Condon theory for approximating atomic energy levels 530</p> <p>22.7 Electron configurations 533</p> <p>Exercises 536</p> <p>Endnotes 538</p> <p>Further reading 538</p> <p><b>23 Introduction to spectroscopy and atomic spectroscopy 539</b></p> <p>23.1 Fundamentals of spectroscopy 540</p> <p>23.2 Time-dependent perturbation theory and spectral transitions 544</p> <p>23.3 The Beer–Lambert law 547</p> <p>23.4 Electronic spectra of atoms 550</p> <p>23.5 Spin–orbit coupling 551</p> <p>23.6 Russell–Saunders (<i>LS</i>) coupling 554</p> <p>23.7 <i>jj</i>-coupling 559</p> <p>23.8 Selection rules for atomic spectroscopy 560</p> <p>23.9 Photoelectron spectroscopy 561</p> <p>Exercises 566</p> <p>Endnotes 569</p> <p>Further reading 569</p> <p><b>24 Molecular bonding and structure 570</b></p> <p>24.1 Born–Oppenheimer approximation 571</p> <p>24.2 Valence bond theory 573</p> <p>24.3 Molecular orbital theory 576</p> <p>24.4 The hydrogen molecular ion H<sup>+</sup><sub>2</sub> 577</p> <p>24.5 Solving the H<sub>2</sub> Schr ¨ odinger equation 580</p> <p>24.6 Homonuclear diatomic molecules 585</p> <p>24.7 Heteronuclear diatomic molecules 588</p> <p>24.8 The variational principle in molecular orbital calculations 591</p> <p>24.9 Polyatomic molecules: The Huckel approximation 593</p> <p>24.10 Density functional theory (DFT) 597</p> <p>Exercises 598</p> <p>Endnotes 601</p> <p>Further reading 601</p> <p><b>25 Molecular spectroscopy and excited-state dynamics: Diatomics 602</b></p> <p>25.1 Introduction to molecular spectroscopy 603</p> <p>25.2 Pure rotational spectra of molecules 604</p> <p>25.3 Rovibrational spectra of molecules 609</p> <p>25.4 Raman spectroscopy 614</p> <p>25.5 Electronic spectra of molecules 617</p> <p>25.6 Excited-state population dynamics 622</p> <p>25.7 Electron collisions with molecules 628</p> <p>Exercises 629</p> <p>Endnotes 632</p> <p>Further reading 633</p> <p><b>26 Polyatomic molecules and group theory 634</b></p> <p>26.1 Absorption and emission by polyatomics 635</p> <p>26.2 Electronic and vibronic selection rules 637</p> <p>26.3 Molecular symmetry 641</p> <p>26.4 Point groups 645</p> <p>26.5 Character tables 647</p> <p>26.6 Dipole moments 650</p> <p>26.7 Rovibrational spectroscopy of polyatomic molecules 652</p> <p>26.8 Excited-state dynamics 656</p> <p>Endnotes 667</p> <p>Further reading 667</p> <p><b>27 Light–matter interactions: Lasers, laser spectroscopy, and photodynamics 668</b></p> <p>27.1 Lasers 669</p> <p>27.2 Harmonic generation (SHG and SFG) 673</p> <p>27.3 Multiphoton absorption spectroscopy 675</p> <p>27.4 Cavity ring-down spectroscopy 682</p> <p>27.5 Femtochemistry 685</p> <p>27.6 Beyond perturbation theory limit: High harmonic generation 688</p> <p>27.7 Attosecond physics 690</p> <p>27.8 Photosynthesis 691</p> <p>27.9 Color and vision 694</p> <p>Exercises 697</p> <p>Endnotes 698</p> <p>Further reading 699</p> <p>Appendix 1 Basic calculus and trigonometry 700</p> <p>Appendix 2 The method of undetermined multipliers 703</p> <p>Appendix 3 Stirling’s theorem 705</p> <p>Appendix 4 Density of states of a particle in a box 706</p> <p>Appendix 5 Black-body radiation: Treating radiation as a photon gas 708</p> <p>Appendix 6 Definitions of symbols used in quantum mechanics and quantum chemistry 710</p> <p>Appendix 7 Character tables 712</p> <p>Appendix 8 Periodic behavior 714</p> <p>Appendix 9 Thermodynamic parameters 717</p> <p>Index 719</p>