# Chemistry 351 and 352 Physical Chemistry I and II

Darin J. Ulness Fall 2006 – 2007

Contents

I Basic Quantum Mechanics 15

16 16 17 17 22 22 23 24 27 27 27 29 30 31 31 34 38 40

1 Quantum Theory 1.1 The “Fall” of Classical Physics . . . . . . . . . . . . . . . . . . . . 1.2 Bohr’s Atomic Theory . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 First Attempts at the Structure of the Atom . . . . . . . . 2 The Postulates of Quantum Mechanics 2.1 Postulate I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 How to normalize a wavefunction . . . . . . . . . . . . . . . . . . 2.3 Postulates II and II . . . . . . . . . . . . . . . . . . . . . . . . . . 3 The 3.1 3.2 3.3 3.4 Setup of a Quantum Mechanical Problem The Hamiltonian . . . . . . . . . . . . . . . . . The Quantum Mechanical Problem . . . . . . . The Average Value Theorem . . . . . . . . . . . The Heisenberg Uncertainty Principle . . . . . .

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4 Particle in a Box 4.1 The 1D Particle in a Box Problem . . . . . . . . . . . . . . . . . . 4.2 Implications of the Particle in a Box problem . . . . . . . . . . . 5 The Harmonic Oscillator 5.1 Interesting Aspects of the Quantum Harmonic Oscillator . . . . . i

5.2 Spectroscopy (An Introduction) . . . . . . . . . . . . . . . . . . .

42

II

Quantum Mechanics of Atoms and Molecules

45

46 46 49 51 52 55 55 56 58 59 60 60 61 62 63 64 66 67 67 68 72 72 73

6 Hydrogenic Systems 6.1 Hydrogenic systems . . . . . . . . . . . . . . . . . . 6.2 Discussion of the Wavefunctions . . . . . . . . . . . 6.3 Spin of the electron . . . . . . . . . . . . . . . . . . 6.4 Summary: the Complete Hydrogenic Wavefunction 7 Multi-electron atoms 7.1 Two Electron Atoms: Helium 7.2 The Pauli Exclusion Principle 7.3 Many Electron Atoms . . . . 7.3.1 The Total Hamiltonian

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8 Diatomic Molecules and the Born Oppenheimer Approximation 8.1 Molecular Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.1.1 The Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . 8.1.2 The Born—Oppenheimer Approximation . . . . . . . . . . 8.2 Molecular Vibrations . . . . . . . . . . . . . . . . . . . . . . . . . 8.2.1 The Morse Oscillator . . . . . . . . . . . . . . . . . . . . . 8.2.2 Vibrational Spectroscopy . . . . . . . . . . . . . . . . . . . 9 Molecular Orbital Theory and Symmetry 9.1 Molecular Orbital Theory . . . . . . . . . . . . . . . . . . . . . . 9.2 Symmetry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 Molecular Orbital Diagrams 10.1 LCAO–Linear Combinations of Atomic Orbitals . . . . . . . . . 10.1.1 Classiﬁcation of Molecular Orbitals . . . . . . . . . . . . .

10.2 The Hydrogen Molecule . . . . . . . . . . . . . . . . . . . . . . . 10.3 Molecular Orbital Diagrams . . . . . . . . . . . . . . . . . . . . . 10.4 The Complete Molecular Hamiltonian and Wavefunction . . . . . 11 An Aside: Light Scattering–Why the Sky is Blue 11.1 The Classical Electrodynamics Treatment of Light Scattering 11.2 The Blue Sky . . . . . . . . . . . . . . . . . . . . . . . . . . 11.2.1 Sunsets . . . . . . . . . . . . . . . . . . . . . . . . . 11.2.2 White Clouds . . . . . . . . . . . . . . . . . . . . . .

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**III Statistical Mechanics and The Laws of Thermodynamics 88
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12 Rudiments of Statistical Mechanics 12.1 Statistics and Entropy . . . . . . . . . . . . . . . . . . . . . . . . 12.1.1 Combinations and Permutations . . . . . . . . . . . . . . . 12.2 Fluctuations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 The Boltzmann Distribution 13.1 Partition Functions . . . . . . . . . . . . . . . . . . . . . . . . . . 13.1.1 Relation between the Q and W . . . . . . . . . . . . . . . 13.2 The Molecular Partition Function . . . . . . . . . . . . . . . . . . 14 Statistical Thermodynamics 15 Work 15.1 Properties of Partial Derivatives 15.1.1 Summary of Relations . 15.2 Deﬁnitions . . . . . . . . . . . . 15.2.1 Types of Systems . . . . 15.2.2 System Parameters . . . 89 89 90 92 94 96 97 99 103 107 107 107 108 108 109

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15.3 Work and Heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 15.3.1 Generalized Forces and Displacements . . . . . . . . . . . 110 15.3.2 P V work . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 16 Maximum Work and Reversible changes 16.1 Maximal Work: Reversible versus Irreversible changes . . 16.2 Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . 16.3 Equations of State . . . . . . . . . . . . . . . . . . . . . 16.3.1 Example 1: The Ideal Gas Law . . . . . . . . . . 16.3.2 Example 2: The van der Waals Equation of State 16.3.3 Other Equations of State . . . . . . . . . . . . . . 113 113 115 116 116 117 118

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17 The Zeroth and First Laws of Thermodynamics 119 17.1 Temperature and the Zeroth Law of Thermodynamics . . . . . . . 119 17.2 The First Law of Thermodynamics . . . . . . . . . . . . . . . . . 121 17.2.1 The internal energy state function . . . . . . . . . . . . . . 121 18 The Second and Third Laws of Thermodynamics 18.1 Entropy and the Second Law of Thermodynamics . 18.1.1 Statements of the Second Law . . . . . . . . 18.2 The Third Law of Thermodynamics . . . . . . . . . 18.2.1 The Third Law . . . . . . . . . . . . . . . . 18.2.2 Debye’s Law . . . . . . . . . . . . . . . . . . 18.3 Times Arrow . . . . . . . . . . . . . . . . . . . . . 124 124 127 127 128 129 130

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IV

Basics of Thermodynamics

134

19 Auxillary Functions and Maxwell Relations 135 19.1 The Other Important State Functions of Thermodynamics . . . . 135 19.2 Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136 19.2.1 Heuristic deﬁnition: . . . . . . . . . . . . . . . . . . . . . . 137

19.3 Helmholtz Free Energy . . . . . . . . . . . . 19.3.1 Heuristic deﬁnition: . . . . . . . . . . 19.4 Gibbs Free Energy . . . . . . . . . . . . . . 19.4.1 Heuristic deﬁnition: . . . . . . . . . . 19.5 Heat Capacity of Gases . . . . . . . . . . . . 19.5.1 The Relationship Between CP and CV 19.6 The Maxwell Relations . . . . . . . . . . . . 20 Chemical Potential 20.1 Spontaneity of processes . . . . . . . . . . . 20.2 Chemical potential . . . . . . . . . . . . . . 20.3 Activity and the Activity coeﬃcient . . . . . 20.3.1 Reference States . . . . . . . . . . . 20.3.2 Activity and the Chemical Potential

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137 138 138 139 139 139 140 142 142 144 146 147 148

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21 Equilibrium 151 21.0.3 Equilibrium constants in terms of KC . . . . . . . . . . . . 153 21.0.4 The Partition Coeﬃcient . . . . . . . . . . . . . . . . . . . 153 22 Chemical Reactions 22.1 Heats of Reactions . . . . . . . 22.1.1 Heats of Formation . . . 22.1.2 Temperature dependence 22.2 Reversible reactions . . . . . . . 22.3 Temperature Dependence of Ka 22.4 Extent of Reaction . . . . . . . 156 156 157 157 158 159 160

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23 Ionics 161 23.1 Ionic Activities . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161 23.1.1 Ionic activity coeﬃcients . . . . . . . . . . . . . . . . . . . 162 23.2 Theory of Electrolytic Solutions . . . . . . . . . . . . . . . . . . . 163

23.3 Ion Mobility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164 23.3.1 Ion mobility . . . . . . . . . . . . . . . . . . . . . . . . . . 165 24 Thermodynamics of Solvation 24.1 The Born Model . . . . . . . . . . . . . . . 24.1.1 Free Energy of Solvation for the Born 24.1.2 Ion Transfer Between Phases . . . . . 24.1.3 Enthalpy and Entropy of Solvation . 24.2 Corrections to the Born Model . . . . . . . . 25 Key Equations for Exam 4 169 170 173 174 174 175 177

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V

Quantum Mechanics and Dynamics

180

26 Particle in a 3D Box 181 26.1 Particle in a Box . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 26.2 The 3D Particle in a Box Problem . . . . . . . . . . . . . . . . . . 183 27 Operators 187 27.1 Operator Algebra . . . . . . . . . . . . . . . . . . . . . . . . . . . 187 27.2 Orthogonality, Completeness, and the Superposition Principle . . 191 28 Angular Momentum 28.1 Classical Theory of Angular Momentum . . 28.2 Quantum theory of Angular Momentum . . 28.3 Particle on a Ring . . . . . . . . . . . . . . . 28.4 General Theory of Angular Momentum . . . 28.5 Quantum Properties of Angular Momentum 28.5.1 The rigid rotor . . . . . . . . . . . . 192 192 193 194 195 199 200

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. . . . . . 209 31 The Two Level System and Quantum Dynamics 211 31.
.1 Symmetry Operators . . . . .
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. . . . . . . . . . . .1 Example: The C2v Group . . . . . . . . . . . . . . . .1 Direct Products . . . . . . . . . . .
. . .2.2 Variational method . . . .29 Addition of Angular Momentum 29. . . . . . 228 33. . . . . . . . . .3 Symmetry of Functions .1 The Two Level System . . .
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VI
Symmetry and Spectroscopy
220
221 222 222 223 223 225 225
32 Symmetry and Group Theory 32. .2 Quantum Dynamics . . . . . . .3.1 Molecular Vibrations . . . . . .2 Normal Modes and Group Theory . . . . . . . . 29. . .
201 201 202 202 203 204 205
30 Approximation Techniques 207 30. . .
.2 Mathematical Groups . . . . . . . . . . . . . . . . . . . . 32. . . . . . .
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33 Molecules and Symmetry 228 33.3 Term Symbols . . . . .2. . . . .1 Spin Angular Momentum . . . . . 207 30. 211 31. . . . . . . . .2 An Example: Two Electrons . . . . . . . . 229
. . . . .1.4 Symmetry Breaking and Crystal Field Splitting
. . . .1 Normal Modes . . . . . . . .
. . . .4 Spin Orbit Coupling . . . . . . 29. . . . . .2. . . . . . . . . . . . . .2. 29. . . . . .
. . . . . . . . . . . General . 32. . . . . . . . . . . . 29. . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Perturbation Theory . . . . . .1 The Addition of Angular Momentum: 29.1. . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . .2. . .2 Addition of Angular Momentum . . . . . . . . . . . . . . . . . . . . . . . . .
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. . .2 Integrated rate laws . . . . 36. .2. . . .
. . . . . . . . . . . . .1 Diﬀerential methods based on the rate law 39. .
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. . 36. . . . . .1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243
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. . . . . . .1 The Structure of the Electronic State 36. . .3 Fluorescence Spectra . . . . . .2. .
. . . . . . . 252 39 The Rate Laws of Chemical Kinetics 39. . . . . . . . . . . . . . . . . . . .1. . . . . . .2 Franck—Condon activity . 231 34. .2 Emission Spectra .1.2 Determination of Rate Laws . . . . . . 36. . .
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. 35. . . . . . . . . . . . . . . . . . . . . .1 kinetic theory of gases . . . .
. . . . . . . . . .2 Rotational Spectroscopy . . . .
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. .34 Vibrational Spectroscopy and Group Theory 231 34. . . . . . . . .
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. . . . . . .2 Raman Spectroscopy . 36 Electronic Spectroscopy of Molecules 36.
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37 Fourier Transforms 245 37. . .
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. . . . . .1 Relaxing the rigid rotor . . . . .1 Rate Laws . . . . . . . . . . . . 36. . .1 Absorption Spectra . . . . .1 The Fourier transformation . . . . . . . . . . . . . .3 Rotation of Polyatomic Molecules . . . . . . . . . 245
VII
Kinetics and Gases
249
38 Physical Kinetics 250 38. . . . . .1. .2 Molecular Collisions . . . . . . . . . . . . . . . . . . . . . . .
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. . .1 Calculation of Entropy . . . . . . . . . . . . .4 Estimation of Virial Coeﬃcients . .2 The Boyle Temperature . . . . . . . . . . . .
. .40 Temperature and Chemical Kinetics 40. .1. . . .
261 261 262 262 265 267 269 269 270 271 272 272 273 274 274 275 275 276 276 279 279 280 281 282 283
41 Gases and the Virial Series 41. . . . . .2 α and κT for liquids and solids . . .
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. . . . . . . . . . . . . . . . .3 The Virial Series in Pressure . . . . . . . . . 40. . 42. . 42. . . . . . . . . .
. . .1 The Relationship Between CP and CV . . . 42. . . . . .
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. . .1 Relation to the van der Waals Equation of State 41. . . . . . . . . . . . . . .1 Temperature Eﬀects on Rate Constants . . . . 40. .1 Temperature corrections to the Arrhenious 40. . . . .2. . . . . . . . . . . . .4 Joule expansion . .5 Joule-Thomson expansion . . . . . . . . . . 42.1 Entropy of Real Gases . . . . . . . . 41. . . . .4 Chain Reactions . . . .
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. . . . . . .2 Heat Capacity of Gases Revisited . . . . 286 43.1 Equations of State . . . . .3. . . . .3 When P is the more convenient variable . . . .2. . . . . . . . . .
. . . . . . . . . .3. .1 Isothermal and Adiabatic expansions . .2. . . . . . . . . . 42. 41. .
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. .1. V and T behavior . . . . . . . . . .3 Expansion of Gases .1 α and κT for an ideal gas . . . . . . . . .1. . . . . 40. . . . . . . 42 Behavior of Gases 42. . . . . . . . . . . . . . .2 The Virial Series . . .2 Heat capacity CV for adiabatic expansions 42. . . . . parameters . . . . . . . . . .
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43 Entropy of Gases 286 43. . . .2 Theory of Reaction Rates . .
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. . . . .4 Henry’s Law .1 Activity (a brief review) 46. . . .3 Ideal Solutions (RL) . . . . . . . . . . 46. . . . 45 Transport Properties of Fluids 45. . .VIII
More Thermodyanmics
292
293 293 294 295 296 296 297 298 298 299 300 301 301 303 305 306 307 308 308 308 309 310 311 311 312 314 316
44 Critical Phenomena 44. . . . . . . . . . . . . .
. . . . .3. .1 Notation . . . . . . . . 45. .1 Diﬀusion . Liquids . . . .
. .3 Thermal conductivity . .
. . . . . . .1 Critical Behavior of ﬂuids . . . . . . . . . . . . . . . . . .
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. . . . . . . . . . . . . . . . . . . . . . .4 Equilibria of condensed phases . 46. . . . . . . . . .2 Partial Molar Volumes . . .
. .3 Reference states for liquids . .5 Triple Point and Phase Diagrams . 44. . . . . . . . 46. . . . .
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. . . . . . . . . . .2 Thermal Conductivity of 46 Solutions 46. . .1 The chemical potential and T and P . . . . . . . . . . . . . . .
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. 44. . . . . .1 Thermal Conductivity of 45. .2 Viscosity . . . . . . . .3.3 Vapor Equilibrium and the Clausius-Clapeyron Equation 44. . . . . . . . . . . . . .
. . . .3. .2 Raoult’s Law . . . . . . . . . . .
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. . . . . . . . . . . . . . . . . . . . .1 Measures of Composition . . .3. . .
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. . . . .1 Gas Laws in the Critical Region . . . . . . . . . . . . . . . . . . . Gases and Solids . .
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. . . . . . . . .2 The Clapeyron Equation . .
. . . . .2. . . 46. 44. .3. . . . . .2 The Law of Corresponding States . . . .
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.3 Phase Equilibrium . . . . 45. . . .
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. . . .1 Freezing Point Depression .3 Examples . . . . . . . . . . . . . . 47. .5 Echo Phenonmena . . . . . . .4. . . .46. . . . . .1 Entropy Production due to Heat Flow . . . . . .
. . . . . . . . .2 Entropy Production due to Chemical Reactions . . . . . . . . . . . . . . . . . . . . . 318 46. . . . . . . . . . . 319 47 Entropy Production and Irreverisble Thermodynamics 47. . . . . . . . . . . . . . . .
. . .3. . . . . . . . . . . . . . . . . . . . . . 47. . . . .2 Osmotic Pressure . . . . . . . . . . . .3. . . 47. . . . . . . . . . . . . . . . . . . . . . . 47. . . . . .
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. . 47. . .4. . . . . . . . . . . . . . . . . . . .2 The Second Law . . . . .4 Thermodynamic Coupling .
.1 Fundamentals . . . . . .4 Colligative Properties . . . . 318 46. . . . . 47. . . . . . 322 322 324 325 326 328 330 331
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Chemistry 351: Physical Chemistry I
1
1
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Solved Problems
I make-up most of the problems on the problems sets. so it might be helpful to you to see some of these problems worked out. This takes time and hard work. But there are some things that you can do to help yourself with these problems. The only way that you can be sure that you understand a concept at to be able to solve the problems associated with it. Simply skip those examples as you scan through this chapter. Even though there aren’t many “book” problems assigned during the year. Keep in mind this chapter provides some examples of how to solve problems for both physical chemistry I and physical chemistry II. you can still learn a lot be working these and looking that their solutions in the solution manual.
Tips for solving problems
Working problem sets is the heart and sole of learning physical chemistry. Tips
2
2
. Consequently early in the course some of the examples might seem very itimidating.

4.1. Budget your time so that you don’t have to work on an overwhelming number of problems at a time. You can do the problem. The only reason you work them is to learn. For problems that require a mathematical approach. 5. • Do not be afraid. • Just identify the general ideas that you think you might need. Then work on them consistently during the week. • Do not worry about not knowing how to solve it yet.. Remember nobody cares if you solve any particular problem on the problem set. There is a tendency to try to start solving the problem before fully understanding the question. If you think you can’t do the problem then maybe you need try a diﬀerent way of thinking about it. Try to ﬁgure out what mathematical techniques you need to express the solution to the problem.
3
. This will make the problem sets much more eﬃcient at helping you learn. 3. They have all been solved before. so if you solve them you will not become famous nor will you save the world. 2. • Read the question carefully • Try to think about what topic(s) in lecture and in the notes the problem is dealing with. • If the question is long. try to identify subsections of it.. Try to whip-oﬀ a few on the same day that you get the problem set. I don’t assign problems that you cannot do. • Determine wether you need to approach the problem mathematically or conceptually or both. Part of the trouble is simply understanding what the problem is asking you to do.

Problems Dealing With Quantum Mechanics
Problem: What is the periodicity of the following functions • f (x) = sin2 x • f (x) = cos x • f(x) = e−2ix Solution: For the ﬁrst function it is easiest to see the periodicity by writing the function as f (x) = (sin x)(sin x). • Always check to see if the math makes sense when you are done. • Make sure that the physical idea that you are using in your argument is correct. We know that this function will repeat zeros when ever sin x = 0. start with a related concept that is better known by you. For problems that require a conceptual approach. Does you ﬁnal answer jive with what you know... sin 2x. either you will be able to do this or you won’t. has a period of π as does the imaginary part. • Look for self-consistency. 6.. If you are not sure. This occurs at x = nπ. n = 0. so the periodicity is π. The second function we should remember from trig as having a period of 2π. Therefore the entire function has a period of π. ±1.
4
. Finally for the last function it is best to used Euler’s identity and write e−2ix = cos 2x + i sin 2x (1)
The real part of this function.• Do the math. cos 2x. . . ±2 . It might take some review on your part.

dx dx
2
(3)
so.Problem: Which of the following functions are eigenfunction of the momentum d operator. What is the probability of ﬁnding the object further than α away from the origin ( x = 0)?
2
5
. this function is not an eigenfunction of the momentum operator. ˆ • ψ(x) = eikx • ψ(x) = e−αx
2
• ψ(x) = cos kx Solution: We need to determine if px ψ(x) = λψ(x) where λ is a constant. dx dx (2)
so. For the case of momentum all we need to do is take the derivative of each function. Problem: A quantum object is described by the wavefunction ψ(x) = e−αx . px = −i~ dx . For the second function px ψ(x) = −i~ ˆ de−αx dψ(x) ↓ 2 = −i~ = 2i~αxe−αx = 2i~αxψ(x). this function is not and eigenfunction of the momentum operator. no. If ˆ this equation is true then the function is an eigenfunction with eigenvalue λ. this function is an eigenfunction of the momentum operator. For the last function z }| { d cos kx dψ(x) = −i~ = −i~k sin kx. For the ﬁrst function px ψ(x) = −i~ ˆ deikx dψ(x) = −i~ = ~keikx = ~kψ(x). px ψ(x) = −i~ ˆ dx dx
6=cos kx
(4)
so. multiply by −i~ and check to see if the eigenvalue equation holds. no. yes.

The ﬁrst integral in the numerator gives the probability that the object is at a position x < −α and the second integral in the numerator gives the probability for x > α. We are interested in ﬁnding the probability that the object is outside of the region −α < x < α. To do this using an unnormalized wavefunction we must evaluate R −α R∞ |ψ(x)|2 dx + α |ψ(x)|2 dx P (|x| > α) = −∞ R∞ . (7)
Solution: First of all we do not know if this wavefunction is normalized. (5) |ψ(x)|2 dx −∞
Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. Normalize this wavefunction.
space
(8)
(9)
6
. but we won’t. (6) e−2αx2 dx −∞ Mathematica can assist with these integrals to give the ﬁnal answer of √ 3 P (|x| > α) = erfc[ 2α 2 ]. The denominator accounts for the fact that the wavefunction is unnormalized. Solution: Following our general procedure from the notes if we have some unnormalized wavefunction. If you were working with a normalized wavefunction the denominator would be equal to 1 and hence not needed. ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm We have shown generally that N is given by sZ N= |ψunnorm (x)|2 dx. The limits of the integral in the denominator represent all space for the object. We could normalize this wavefunction. so we should assume that it isn’t. Plugging in the wavefunctions we have R −α −2αx2 R∞ 2 e dx + α e−2αx dx −∞ R∞ P (|x| > α) = .

2γ
Problem: What is the probability of ﬁnding an electron in the 1s state of hydrogen further than one Bohr radius away from the nucleus? Solution: We need to evaluate Z P (r > a0 ) =
2π
0
Z
π
0
Z
∞
a0
|ψ1s |2 r2 sin θdrdθdφ. 2γ
(13)
So on average you will ﬁnd the object at x =
1 . What is the average position of the object? Solution: We need to work with the normalized wavefunction that we found in √ the previous problem. The normalized 1s wavefunction is 1 ψ1s = p 3 er/a0 . o (12) hˆi = o
space
which in this case is Z ∞p Z p −γx −γx hˆi = x 2γe x 2γe dx = 2γ
0
∞
xe−2γx dx =
0
1 . Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. Generally and average is calculated as Z ψ∗ (x)ˆψ(x). πa0 (15)
7
.Which for this case is N=
sZ
∞
0
|e−γx |2
dx =
sZ
∞
e−2γx dx
=
0
r
1 2γ
(10)
So ﬁnally we get the normalized wavefunction by rearanging ψunnorm = Nψnorm : p (11) ψnorm (x) = 2γe−γx . ψ(x) = 2γe−γx .
(14)
Remember the extra r2 sin θ is needed when integrating in spherical polar coordinates.

(19)
8
. Express the wavefunction (in Cartesian coordinates) as a product 2m state. but all it is asking is to express the wavefunction. e2 (16)
So. What is the force constant associated with the Morse potential? Solution: The Morse potential is £ ¤ V (x) = De 1 − e−β(R−Req ) . z) = ψ(x)ψ(y)ψ(z). 2 ˆ H = −~ ∇2 . y. Problem: A free particle in three dimensions is described by the Hamiltonian. Verify that the coeﬃcient for the linear term is zero. Therefore the appropriate product state is Ψ(x. We know that if the wavefunction is to be a product state then the Hamiltonian must be made up of a sum of independent terms. Ψ(x. To see this we write out the Laplacian to get µ ¶ −~2 ∂ 2 ∂2 ∂2 ˆ H= . z) as a product state.We can do this integral by hand or have Mathematica help us to give P (r > a0 ) = 5 = 0. about 68% of the time the electron would be found at some distance greater then one Bohr radius from the proton. (17) + + 2m ∂x2 ∂y 2 ∂z 2 We see that indeed the Hamiltonian is a sum of term that depends only on x. y.677. a term depending only on y and a term that depends only on z. Solution: This problem appears hard at ﬁrst since we are not studying three dimensional systems. (18)
Problem: Expand the Morse potential in a Taylor’s series about Req . which is a function of the three spatial dimensions.

Hence no mater what the vibrational quantum number is there is just as much of the wavefunction on either side equilibrium thus hRi = Req for any quantum number. yes the coeﬃcient of the linear term (the term involving (R − Req ) to the ﬁrst power) is zero. The force constant is given by the coeﬃcient of the quadratic term so in this case k = β 2 De . It is steeper on the “short” side of equilibrium and softer on the “long” side of equilibrium and this “softness” increases with increasing quantum number. (20) V (x) = V (x)|Req + dx ¯Req 2! dx2 ¯Req | {z } | {z } | {z } =0
=0 = β 2 De
Problems Dealing With Statistical Mechanics and Thermodynamics
Problem: A vial containing 10 20 benzene molecules is at 300K. Problem: Without performing any calculations. The potential for the harmonic oscillator is described by a parabola centered about the equilibrium bond length.So. compare hRi as a function of the vibrational quantum number for a diatomic modelled as a harmonic oscillator versus a Morse oscillator. Solution: This problem requires the we think qualitatively about the wavefunctions and the potentials for the harmonic oscillator and the Morse oscillator. The Morse potential does not have this symmetry. Therefore without performing any calculations we can at least say that hRi increases as the quantum number increases.
The Taylor series about Req for this function is ¯ ¯ 2 ¯ dV (x) ¯ ¯ (R − Req ) + 1 d V (x) ¯ (R − Req )2 + · · · . This will always be true when you perform a Taylor series expansion about a minimum (or maximum). How many molecules are in the ﬁrst excited state of the ‘ring breathing’ mode (992 cm −1 )? How
9
.

02 × 1013 .41×10 × 100% = 0. Problem: Consider a linear chain of N atoms. Find the entropy per atom for this system as N → ∞.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and
C—H Nv=1
We see that about 8. Each of the atoms can be in one of three states A. For example. V (j+1) = MV (j) . B or C.many are in the ﬁrst excited state of the symmetric C—H vibrational mode (3063 cm −1 )? Solution: This is a problem that deals with the Boltzmann distribution.··· . except that an atom in state A can not be adjacent to an atom in state C.0000402% of the benzene molecules are in the ﬁrst excited state for the C—H stretching mode. 0 1 1 ⎡ (24)
¶ ³ µ ´ 3063 − 3×3063 2×208 × 1020 = 4. 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation. where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦. So. B or C. ⎡ ⎤ ⎡ ⎤ ⎡ ⎤ 1 2 5 ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ (1) (2) (3) (23) V = ⎣ 1 ⎦. To solve this problem it is useful to deﬁne the set of three dimensional column vectors V (j) such that the three elements are the total number of allowed conﬁgurations of a j-atom chain having the j th atom in state A.02×10 × 100% = 1020 0. V = ⎣ 7 ⎦. × e = 2 sinh 2 × 208
17
(22)
(25)
10
.841% of the benzene molecules are in the 1020 13 ﬁrst vibrational excited state for the ring breathing mode and 4. V = ⎣ 3 ⎦. ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8.

3. 4. It can be shown that the number of conﬁgurations W = Tr[M N ].
For part (b) we need to list all states for the case of N = 3 and verify the we get the same result as calculated using the transfer matrix. max where λmax is the largest eigenvalue of M. Verify W = Tr[M N ] for N = 1 and N = 2. Use M to ﬁnd V (4) 2. Use Boltzmann’s equation to ﬁnd the entropy per atom for this chain as N goes to inﬁnity. Tr[M N ] ≈ λN . max
N→∞
(26)
1. 12 5 1
. So W = lim λN . Remembering that V (3) gives us the number of sequences that end in a given state we should organize our list in the same manner States ending in A States ending in B AAA ABA BAA BBA CBA AAB ABB BAB BBB BCB CBB CCB √ 7 states States ending in C ABC BBC BCC CBC
Solution: For part (a) we simply problem (we are given V (3) ): ⎡ 1 1 ⎢ (4) V =⎣ 1 1 0 1
use the transfer matrix as directed in the ⎤ ⎤⎡ ⎤ ⎡ 12 5 0 ⎥ ⎥⎢ ⎥ ⎢ 1 ⎦ ⎣ 7 ⎦ = ⎣ 17 ⎦ . Now for large N.The matrix M is the so-called transfer matrix for this system. Verify V (3) explicitly by drawing all the allowed 3-atom conﬁgurations.
5 states
√
5 states
√
11
.
1.

Therefore the limiting entropy per atom is ³ √ ´ S = k ln 1 + 2 . Assume benzene has only two active modes (992cm −1 and 3063cm −1 ) and assume the Laser light used to do the scattering is at 20000cm −1 (this is 500nm–green light). For part (c) we evaluate W = Tr[M N ] for N = 1 and 2. Solution: Since there are two vibrational modes we expect two Stokes lines to the red of 20000cm−1 . There is only one Rayleigh line and it is at the same frequency at the input laser beam which. Likewise we expect two anti-Stokes lines. For part (d) we use S k k k = ln W = lim ln λN = lim N ln λmax = k ln λmax .States like AAC are not allowed because A and C are neighbors. is 20000cm−1 . Using √ Mathematica we ﬁnd λmax = 1 + 2. and C. one at 20000cm−1 − 992cm−1 = 19008cm−1 and one at 20000cm−1 − 3063cm−1 = 16937cm−1 . B. W = Tr[M] = 3 This corresponds to the three distinguishable microstates A. we simply need to ﬁnd the maximum eigenvalue of the Transfer matrix. calculate the positions of the Rayleigh. ⎤⎤ ⎡⎡ ⎤⎤ ⎤⎡ ⎡⎡ 2 2 1 1 1 0 1 1 0 ⎥⎥ ⎢⎢ ⎥⎥ ⎥⎢ ⎢⎢ W = Tr[M 2 ] = Tr ⎣⎣ 1 1 1 ⎦ ⎣ 1 1 1 ⎦⎦ = Tr ⎣⎣ 2 3 2 ⎦⎦ = 7 (27) 0 1 1 0 1 1 1 2 2 This corresponds to the seven distinguishable microstates AA. BB. max N→∞ N N→∞ N N N
(28)
So. BC. (29) N Problem: Using the classical theory of light scattering.
12
. Stokes and anti-Stokes spectral lines for benzene. BA. For N = 1. CB and CC (Remember C and A cannot be neighbors). in this case. one at 20000cm−1 + 992cm−1 = 20992cm−1 and one at 20000cm−1 + 3063cm−1 = 23063cm−1 . For N = 2. AB.

and U from the partition function for this model. Ã ! 1 N Qcrystal = qHO = (30) 2 sinh β~ω 2 From our formulas for statistical thermodynamics ¶ µ β~ω . Writing out the total derivative of U(T.Problem: A simple model for a crystal is a “gas” of harmonic oscillators. V ). V ) we get ¶ ¶ µ µ ∂U ∂U dT + dV. V − nb T V 2 (34)
We are interesting in an equation of state for U(T. S. Determine A. S = −kβ ∂Qcrystal + k ln Qcrystal ∂β µ ¶ β~ω β~ω Nkβ~ω coth − k ln 2 sinh = 2 2 2 U =− (32)
and
N~ω β~ω ∂Qcrystal = coth . (35) dU = ∂T V ∂V T
13
. Solution: The equation representing a Berthelot gas is P = nRT n2 a − . (33) ∂β 2 2 Problem: Express the equation of state for internal energy for a Berthelot gas. Solution: For this model the crystal is modelled as a collection of harmonic oscillators so we need the partition function for the harmonic oscillator. A = −kT ln Qcrystal = +NKT ln 2 sinh 2
(31)
where we used properties of logs to pull the N out front and move the sinh term from to the numerator.

but ∂V T is nothing convenient so we must ∂T proceed. Cp = Cv − T ∂T P ∂V T
(41)
14
.¡ ¢ ¡ ∂U ¢ Now ∂U V is just heat capacity. ¶2 µ ¶ µ ∂P ∂V .
(40)
P
This eliminates the constant V term and so. We employ the “useful relation” µ ¶ ¶ µ ∂U ∂P =T −P (36) ∂V T ∂T V to eliminate U in favor of P so that we can use the equation of state for a Berthelot gas. (37) ∂T V V − nb T V V − nb T V 2 TV 2 Hence the equation of state for internal energy of a Berthelot gas is dU = CV dT + 2n2 a dV TV 2 ¡ ∂P ¢ (38)
Problem: Use the identities for partial derivatives to eliminate the in ¶ µ ¶ µ ∂P ∂V Cp = Cv + T ∂T P ∂T V so that all derivatives are at constant pressure or temperature.
∂T V
factor (39)
Solution: Here we either remember an identity or turn to our handout of partial ¡ ¢ derivative identities to employ the cyclic rule to ∂P V : ∂T µ ∂P ∂T ¶
V
∂P =− ∂V
µ
¶ µ
T
∂V ∂T
¶
. CV . One obtains ¶ µ ¶ µ n2 a n2 a ∂P nRT nR 2n2 a + 2 2 − + T −P =T = .

Part I Basic Quantum Mechanics
15
15
.

1. Quantum Theory
The goal of science is uniﬁcation. The photoelectric eﬀect 2.1. Among these experiments were 1. Atomic spectral lines 4. The “Fall” of Classical Physics
A good theory: • explain known experimental results • self consistent • predictive • minimal number of postulates Around the turn of the century. • Many phenomena described by minimal and general concepts. Low temperature heat capacity 3. experiments were being performed in which the results deﬁed explanation by means of the current understanding of physics. Black body radiation and the ultraviolet catastrophe 16
16
.1.

2.
Flaws of the solar system model • Newton: OK √ √
• Maxwell: problem
17
.5. First Attempts at the Structure of the Atom The “solar system” model. The two slit experiment 6.1.2. • The electron orbits the nucleus with the attractive coulomb force balanced by the repulsive centrifugal force. The Stern-Gerlach experiment
∗ ∗ See Handouts ∗ ∗
1. Bohr’s Atomic Theory
1.

— The system is not stable and the electron spirals into the nucleus. the atom acts as an oscillating dipole
•
— The classical theory of electromagnetism states that oscillating dipoles emit radiation and thereby lose energy.— As the electron orbits the nucleus. The atom collapses!
Bohr’s model: Niels Bohr (1885—1962)
18
.

2)
19
. me and e are the mass and charge of the electron respectively and 0 is the permittivity of free space.• Atoms don’t collapse =⇒ what are the consequences Experimental clues • Atomic gases have discrete spectral lines.3) Eionize = E∞ − E1 = 2a0 ∞2 1 2a0
(1. EN = −Z 2a0 N 2 Tests of the Bohr atom • Ionization energy of Hydrogen atoms — The Ionization energy for Hydrogen atoms (Z = 1) is the minium energy required to completely remove an electron form it ground state. me e2 The total energy of the Bohr atom is related to its quantum number µ 2 ¶ e 1 2 ..e.
2
The constant quantity 4π e0e~ appears often and is given the special symbol a0 ≡ m 2 4π 0 ~2 = 0. ~ = h/2π is Planck’s constant divided by 2π. • Therefore atomic orbitals must be quantized. N = 1 → N = ∞ µ ¶ 1 e2 −Z 2 e2 1 − 2 = (1. i.1) Zme e2 where Z is the atomic number. r=
4π 0 N 2 ~2 (1. N is a positive real integer called the quantum number.52918 Å and is called the Bohr radius. • If the orbital radius was continuous the gas would have a continuous spectrum.

5. R is called the Rydberg constant.4)
— Since the orbitals are quantized. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1.e — Eionize = 2a0 = 13.606 eV = 109.· · · 6.4.8.7.
2
— Eionize experimentally observed from spectroscopy is 13.· · · 3.5. the atom may only change its orbital radius by discrete amounts.· · · Series Name Lyman Balmer Pachen Brackett Pfund
(1.605 eV (very good agreement) • Spectroscopic lines from Hydrogen represent the diﬀerence in energy between the quantum states — Bohr theory: Diﬀerence energies µ ¶ µ ¶ 1 1 e2 1 1 Ej − Ek = − 2 =R − 2 2a0 Nj2 Nk Nj2 Nk Initial state Nk 1 2 3 4 5 • Final States Nj 2.6.· · · 5.7.667 cm−1 = R.6.3.· · · 4.4.5)
Failure of the Bohr model • No ﬁne structure predicted (electron-electron coupling) • No hyperﬁne structure predicted (electron-nucleus coupling) • No Zeeman eﬀect predicted (response of spectrum to magnetic ﬁeld)
20
.

• Spin is not included in theory The Bohr quantization idea points to a wavelike behavior for the electron. The wave must satisfy periodic boundary conditions much like a vibrating ring ∗ ∗ ∗ See Fig. 11.9 Laidler&Meiser ∗ ∗∗ The must be continuous and single valued Particles have wave-like characteristics The Bohr atom was an important step towards the formulation of quantum theory • Erwin Schrödinger (1887—1961): Wave mechanics • Werner Heisenberg (1902—1976): Matrix mechanics • Paul Dirac (1902—1984): Abstract vector space approach
21
.

x. y and y +dy and z and z +dz is |ψ(x. Postulate I
Postulate I: The state of a system is deﬁned by a wavefunction. in fact. We will normally take ψ to be a complex valued function of time and coordinates: ψ(t. That is. z) at the position between x and x+dx. ψ. be a function of momentum. The Postulates of Quantum Mechanics
2. θ. which contains all the information that can be known about the system. y. represents a probability distribution which is directly observable. The wavefunction ψ represents a probability amplitude and is not directly observable. z)|2 dxdydz (or |ψ(r. y. y. φ)|2 r2 sin θdrdθdφ in spherical coordinates). z) Note: In general the wavefunction need not be expressed as a function of coordinate.2.1. y. It may. 22
22
. the probability of ﬁnding a particle which is described by ψ(x. However the mod-square of the wavefunction. we will most often deal with time independent “stationary” states ψ(x. for example. ψ∗ ψ = |ψ|2 . z) and.

z)|2 dxdydz space R This assures that space |ψnorm |2 dxdydz = 1 as expected for a probability distribution From now on we will always normalize our wavefunctions.1) Now.Properties of the wavefunction • Single valueness • continuous and ﬁnite • continuous and ﬁnite ﬁrst derivative R • space |ψ(x. y. y.
2. ψ(x. y. (2. z) must be normalizable. z)|2 to be exactly interpreted as a probability distribution. z)|2 dxdydz < ∞ Normalization of the wavefunction In order for |ψ(x. where N = |ψunnorm (x. y. qR That is.2. How to normalize a wavefunction
If we have some unnormalized wavefunction. (2.2)
space space
23
. ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm . we take the mod-square of both sides and then integrate both sides of this equation over all space Z Z 2 |ψunnorm | dxdydz = |Nψnorm |2 dxdydz. ψ unnorm = Nψnorm .

24
. therefore this is a general procedure that will work for any wavefunction.
(2.3)
space space
because that is the very deﬁnition of a normalized wavefunction. N unnorm (2. y.6)
So ﬁnally we get the normalized wavefunction by reagranging ψ unnorm = Nψnorm : ψ norm = 1 ψ . Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1. (2.4)
This gives us an expression for N. So. (2.7)
Notice that no where did we ever specify what ψunnorm or ψnorm actually were. sZ N=
space
|ψunnorm (x. To ﬁnd the probability for the particle to be in a ﬁnite region of space we simple evaluate (here a 1D case) R x2 Z x2 |ψ(x)|2 dx if ψ(x) x1 P (x1 < x < x2 ) = R ∞ =⇒ |ψ(x)|2 dx (2.but
The N is just a constant so it can be pulled out of both the mod-square and the integral Z Z 2 2 |ψunnorm | dxdydz = N |ψnorm |2 dxdydz. Taking the square root of both sides gives.3.5)
space
Z
space
|ψnorm |2 dxdydz = 1
(2. Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 . z)|2 dxdydz.8) 2 normalized x |ψ(x)| dx 1 −∞
2. Postulates II and II
Postulate II: Every physical observable is represented by a linear (Hermitian) operator.

10)
25
. cylindrical. These functions are called eigenfunctions.). (2. For a given operator only a special set of function satisfy this equation.An operator takes a function and turns it into another function ˆ Of (x) = g(x) (2. Nearly all operators we will need are algebraic combinations of the above. So in quantum mechanics operators act on the wavefunction to produce a new wavefunction The two most important operators as far as we are concerned are • x=x ˆ
∂ • px = −i~ ∂x ˆ
and of course the analogous operators for the other coordinates (y. There is a special operator equation called the eigenvalue equation which is ˆ Of (x) = λf (x) where λ is just a number. z) and coordinate systems (spherical. etc. Postulate III: The measurement of a physical observable will give a result that is one of the eigenvalues of the corresponding operator.9)
This is just like how a function takes a number and turns it into another number.

The number that goes with each function is called the eigenvalue. Example ˆ ˆ Let O in the eignevalue equation be the operator that takes the derivative: O = ˆ d d = dx . So the eigenfunctions are the set of functions f (x) = eλx and the eigenvalues are the numbers λ
26
.11)
So. we ask ourselves what function is proportional to its own derivative? ⇒ f (x) = eλx . So solution of the eigenvalue equation gives a set of eigenfunctions and a set of eigenvalues. So we want a solution to ˆ df (x) = λf (x) df (x) = λf (x) dx (2.

2. The Quantum Mechanical Problem
Nearly every problem one is faced with in elementary quantum mechanics is handled by the same procedure as given in the following steps. This equation is the (time independent) Schrödinger equation. Deﬁne the classical Hamiltonian for the system.1.1)
3. 1. The eigenvalue equation for the Hamiltonian is ˆ Hψ = Eψ. This equation is the most important equation of the course and we will use it many times throughout our discussion of quantum mechanics and statistical mechanics.3. 27
27
. The operator associated with the total energy is called the Hamiltonian operator ˆ (or simply the Hamiltonian) and is given the symbol H. The Setup of a Quantum Mechanical Problem
3. (3. The Hamiltonian
The most important physical observable is that of the total energy E.

which is now a second order diﬀerential equation of the form ¸ ∙ 2 −~ 2 ∇ + V (x. z) H =T +V = 2m
(3.3)
• The potential energy is almost always a function of coordinates only V = V (x.6)
ˆ V = V (ˆ.7)
ˆ 3. x ˆ ˆ So.8) ⇒ 2m
28
. x. Use Postulate II to replace the classical variables. z) (3. Thus. y. y. z). ∂z 2
and (3. y . Hψ = Eψ. where T is the kinetic energy and V is the potential energy. y. y. z ) = V (x. z) − E) ψ = 0 (3. with their appropriate operators. z) ψ = Eψ 2m −~2 2 ∇ ψ + (V (x. • The kinetic energy is always of the form T = ¢ 1 ¡ 2 px + p2 + p2 y z 2m (3. px etc. ˆ T = 2m 2m
(3.• The total energy for a classical system is Ecl = T + V. Solve the Schrödinger equation. y.5)
where ∇2 ≡
∂2 ∂x2
+
∂2 ∂y2
+
∂2 ..4)
• Note: Some quantum systems don’t have classical analogs so the Hamiltonian operator must be hypothesized.
2 2 ˆ −~ ∇2 = −~ ∇2 . −~2 2 ˆ ˆ ˆ ∇ + V (x. 2.2)
(3.

• Note: It is solely the form of V (x. or average. z) which determines whether this is easy or hard to do. however. then all measurements of that physical property will yield the associated eigenvalue.12)
space
29
. We can.3. hˆi = x and hˆx i = p Z Z ψ xψdxdydz = ˆ
∗
space
Z
space
x |ψ|2 dxdydz ψ∗ ∂ψ dxdydz ∂x
(3. value for the measurement.11)
space
ψ px ψdxdydz = −i~ ˆ
∗
Z
(3. then all measurements of that physical property will still yield an eigenvalue. y. give an expectation. • For one-dimensional problems −~2 d2 ψ + (V (x) − E) ψ = 0 2m dx2 (3.10)
space
For example. This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3. If ψ is not an eigenfunction of a particular operator.9)
3. but we cannot predict for certain which one. However. The Average Value Theorem
Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable.

β ˆ ˆˆ ˆˆ (3. for example. we can 2 know. even in principle. We see δpx δx ≥ 1 1 |h[ˆx . The commutator is ˆ where the notation α.3. β ˆ ˆ deﬁned as h i ˆ ≡ αβ − β α.15)
So.b. the y position and the x momentum to arbitrary precision. The general statement of the Heisenberg uncertainty principle is 1 ¯Dh ˆ iE¯ ¯ ¯ δαδβ ≥ ¯ α. x]i| = |hˆx x − xpx i| p ˆ p ˆ ˆˆ 2 ¯Z 2 ¯ µ ¶ ¯ 1¯ ¯ ψ ∗ ~ ∂ x − x ∂ ψdx¯ = ¯ 2¯ i ∂x ∂x ¯ ¯ ¯~¯ ~ = ¯ ¯= .14) The most important example of complimentary variables is position and momentum. α.4. δpx δy = 0. β ¯ . Such variables are called complimentary. be simultaneously known to arbitrary precision.. ¯ 2i ¯ 2 (3. ˆ (3.13) 2 h i ˆ means the commutator of α and β.) Suppose we know the position of a particle perfectly. (n. This idea is the Heisenberg uncertainty principle and is of profound importance. at the very best we can only hope to simultaneously know position and momentum such that the product of the uncertainty in each is ~ . The Heisenberg Uncertainty Principle
In quantum mechanics certain pairs of variables can not. what can we say about its momentum?
30
.

4.1)
Because of the inﬁnities at x = 0 and x = a. It also can be used as a “zeroth order” model for certain physical systems. we need to partition the x-axis into the three regions shown in the ﬁgure.
31
31
. shown in the ﬁgure and given by ⎧ x≤0 ⎪ ∞ ⎨ V (x) = 0 0<x<a .1. This system is very simple which is one reason for beginning with it. Particle in a Box
We now will apply the general program for solving a quantum mechanical problem to our ﬁrst system: the particle in a box. Nevertheless it is of great pedagogical and practical value. ⎪ ⎩ ∞ x≥a
(4. as a consequence. We shall soon see that the particle in a box is a physically unrealistic system and. The 1D Particle in a Box Problem
Consider the potential.4. we must violate one of our criteria for a good wavefunction. V (x).

The particle must be found only in region II.Now.c. dx2 ~ The general solution of this diﬀerential equation is ψ(x) = A sin kx + B cos kx. the particle can never exist so. in region I and III. where k = q
2mE . Hψ 2m dx2
(4. ~2
(4.4)
Now ψ must be continuous for all x. where the potential is inﬁnite.
32
. Therefore it must satisfy the boundary conditions (b.3)
(4.2)
which can be rearranged into the form d2 ψ(x) 2mE + 2 ψ(x) = 0. ψ must equal zero in these regions.): ψ(0) = 0 and ψ(a) = 0. The Schrödinger equation in region II is (V (x) = 0)
2 2 ˆ = Eψ =⇒ −~ d ψ(x) = Eψ.

a
(4. this becomes a Z π π A2 a a/ 2a = .5)
(4. So.c. 3. We obtain A from Z ∞ Z a nπx nπx ∗ sin dx.c. the second b. now we have nπx . places certain restrictions on k. So we are left with ψ(x) = A sin kx for our wavefunction. we see that the constant B must be zero because cos kx|x=0 = 1. n = 1. As can be inferred from the following ﬁgure. · · · .
In particular.6)
The constant A is the normalization constant. ψn (x)ψ n (x) = 1 = A2 sin a a −∞ 0 Letting u =
πx . 2.8)
33
. 1=A sin2 nudu = A2 π 0 2 / 2 π
(4. a The values of k are quantized..
nπ .From the ψ(0) = 0 b. ψn (x) = A sin a kn =
(4.7)
du = π dx. ψ(a) = 0.

a in a box are I II III .Solving for A gives A=
r
2 .2.9)
Is this wavefunction OK?
Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q
2mEn ~2
(4. 2ma2 8ma2
(4.11)
4. Implications of the Particle in a Box problem
Zero Point Energy
34
.10)
We can get the energy levels from kn = En =
and kn =
nπ : a
h n2 π 2 ~2 ~= 2π n2 h2 = .
(4.

But we also know that the particle is located within a ﬁnite region of ˆ space. If the energy was zero then we would conclude that momentum was exactly zero. x ˆ Features of the Particle in a Box Energy Levels • The energy level spacing is 4E = En+1 − En = 4E = (2n + 1) (n + 1)2 h2 n2 h2 h2 − = (n2 + 2n + 1 − n2 ) / / 8ma2 8ma2 8ma2 (4. or ground state.The smallest value for n is 1 which corresponds to an energy of E1 = h2 6= 0. This residual energy is called the zero point energy and is a consequence of the uncertainty principle. δˆδp = 0 which violates the uncertainty principle. δ p = 0. so δˆ 6= ∞. the lowest energy state. has nonzero energy.13)
h2 8ma2
• This spacing increases linearly with quantum level n • This spacing decreases with increasing mass • This spacing decreases with increasing a • It is this level spacing that is what is measured experimentally The Curvature of the Wavefunction
35
. x Hence.12)
That is. 8ma2 (4.

We also know that the wave function is not zero everywhere. This is an important concept for the qualitative understanding of wavefunctions for any quantum system. As another example consider the expectation value of position for a particle in the second quantum level: Z ∞ Z a 2 a 2π ∗ hxi = (4. dx2
From freshman calculus we know that the second derivative of a function describes its curvature so. • We know the wavefunction is zero in regions I and III. We have already seen such nonclassical behavior as quantized energy and zero point energy. the wavefunction is less conﬁned and so the curvature does not need to be as great to satisfy the boundary conditions. a wavefunction with more curvature will have a larger second derivative and hence it will posses more kinetic energy. Therefore the energy levels decrease in energy as does their diﬀerence.ˆ The operator for kinetic energy is T =
−~ 2 d2 . Therefore it must do something between x = 0 and x = a.14) ψ2 (x)xψ 2 (x)dx = x sin2 [ x]dx = a 0 a 2 −∞
36
. The particle in a box problem illustrates some of the many strange features of quantum mechanics. 2m dx2
The important part of this is
d2 . It must have some curvature and hence some zero point energy. Applying this idea to the particle in a box we an anticipate both zero point energy and the behavior of the energy levels with increasing a. • As a is increased.

So even though the particle may be found anywhere else in the box and it may get from the left side of the node to the right side.
37
. it can never be found at the node.yet the probability of ﬁnding the particle at x = a is zero: ψ2 ( a ) = 0. There is 2 2 a a node at x = 2 .

We shall begin by reviewing the classical harmonic oscillator and than we will turn our attention to the quantum oscillator. where k is the spring constant and Req is the equilibrium position of the ball.5. Setting x = R − Req we can measure the displacement about the equilibrium position. The Harmonic Oscillator
The harmonic oscillator model which is simply a mass undergoing simple harmonic motion. The classical example is a ball on a spring
The harmonic oscillator is arguably the single most important model in all of physics. The force exerted by the spring in the above ﬁgure is F = −k(R − Req ). 38
38
.

E. we need to express the force of the spring in terms of potential energy V . P. where ω = conditions. 2 By postulate III the Schrödinger equation becomes ⎛ ⎞
K.2)
and A and B are constants which are determined by the initial
For quantum mechanics it is much more convenient to talk about energy rather than forces. so in going to the quantum oscillator.
39
.E. (5. we get dt
2
d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m
(5. We know Z 1 V = − F dx = kx2 + C.1)
This is second order diﬀerential equation which we already know the solutions to: x = A sin ωt + B cos ωt. 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2
(5.5)
This diﬀerential equation is not easy to solve (you can wait to solve it in graduate school).x From Newton’s law of motion F = ma = m d 2 . q
k m
(5.4)
(5.
This can be rearrange into the form −~2 d2 ψ + 2m dx2
1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ.3) 2 Since energy is on an arbitrary scale we can set C = 0. Thus V = 1 kx2 .

The equation is very close to the form of a know diﬀerential equation called Hermite’s diﬀerential equation the solutions of which are called the Hermite polynominals. the solutions (the eigenfunctions) to the Schrödinger equation for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψn (y) = An Hn (y)e . 2 where ν 0 =
1 2π
(5. ∗ ∗ ∗ See Fig. 11. An = p √ . 2 where again ω = q
k . The eigenvalues (the energy levels) are 1 En = (n + )~ω. As it turns out.6) x.7)
Note the energy levels are often written as 1 En = (n + )hν 0 . y = (5.8)
q
k m
and is called the vibrational constant. 2 ~ 2n n! π
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.1. Interesting Aspects of the Quantum Harmonic Oscillator
It is interesting to investigate some of the unintuitive properties of the oscillator as we have gone quantum mechanical
40
. m
(5.12 Laidler&Meiser ∗ ∗∗
5.

the quantum system must behave like a classical system. then we would conclude that the momentum of the oscillator was zero. this energy is called the zero point energy. • It is a consequence of uncertainty principle — If the ground state energy was really zero. — On the other hand.1. so δpδx = 0 Not allowed! — The uncertainty principle forces there to be some residual zero point energy. 3. In other words the quantum mechanics must contain classical mechanics as a limit. • The wavefunctions penetrate into the region where the classical particle is forbidden to go — The wavefunction is nonzero past the classical turning point. we would conclude the particle was located at the bottom of the potential well (at x = 0) — Thus we would have δp = 0. Interpretation of the wavefunctions and energy levels
41
. 2 • Just like for the particle in a box. Consider the ground state (the lowest energy level) • There is residual energy in the ground state because 1 E0 = (0 + )~ω. • The probability distribution |ψ|2 becomes more and more like what is expected for the classical oscillator when v → ∞. Consider the wavefunctions. — This is a manifestation of the correspondence principle which states that for large quantum numbers. 2. δx = 0.

• Remember the wavefunctions are time independent and the energy levels are stationary • If a molecule is in a particular vibrational state it is NOT vibrating. Experiments involving electromagnetic radiation—matter interaction are called spectroscopies.
42
. These speciﬁc values correspond to the energy level diﬀerence between the initial and ﬁnal states.2.
5. Spectroscopy (An Introduction)
The primary method of measuring the energy levels of a material is through the use of electromagnetic radiation. Atoms and molecules absorb or emit light only at speciﬁc (quantized) energies.

10)
• The Schrödinger equation (which should be posted on your refrigerator). N unnorm (5. ˆ Hψ = Eψ. This section should not substitute for your studying of the rest of this material.
Equations
• The short cut for getting the normalization constant (1D. sZ N=
space
|ψunnorm (x)|2 dx. (5. The equations are collected here simply for handy reference for you while working the problem sets.Key Equations for Exam 1
Listed here are some of the key equations for Exam 1.9)
• The normalized wavefunction: ψ norm = 1 ψ .
(5.11)
43
43
. see above for 3D). The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.

16)
• The energy level spacing for the 1D particle in a box. ω = 2
k m
(5.12)
(5. a a • The energy levels for the 1D particle in a box. y = √ . r nπx 2 ψn (x) = sin . 2m dx2 • How to get the average value for some property (1D version).14)
• Normalized wavefunctions for the 1D particle in a box. −~2 d2 ψ + (V (x) − E) ψ = 0.19)
44
.17)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x.• The Schrödinger equation for 1D problems as a diﬀerential equation.15)
(5. En =
h n2 π 2 ~2 ~= 2π n2 h2 = . ∂x
(5. 2ma2 8ma2
(5. r
• The energy levels are 1 En = (n + )~ω. 2 n n! π ~ 2
(5. An = p ψn (y) = An Hn (y)e . ˆ hˆ i = α
space
(5. 4E = (2n + 1) h2 8ma2 (5.18)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. Z ψ∗ αψdx.13)
• The momentum operator
px = −i~ ˆ
∂ .

Part II Quantum Mechanics of Atoms and Molecules
45
45
.

6. The Hydrogen atom (one proton and one electron) is the obvious example Ions such as He+ and Li2+ are also hydrogenic systems. Hydrogenic systems
Hydrogenic systems are those atomic systems which consist of a nucleus and one electron. So this will be the ﬁrst atomic system we discuss. These system are centrosymmetric. Hydrogenic Systems
Now that we have developed the formalism of quantum theory and have discussed several important systems. The obvious choice for the coordinate system is to use spherical polar coordinates
46
46
.1. we move onto the quantum mechanical treatment of atoms. Hydrogen is the only atom for which we can exactly solve the Schrödinger equation for. The Schrödinger equation for all the other atoms on the periodic table must be solved by approximate methods.6. That is they are completely symmetric about the nucleus.

∇ + H= 2me (4π 0 )ˆ r
(6.7)
47
. ψ must be a product state.1)
−Ze2 −~2 ˆ 2 ˆ . (4π 0 )r (6. φ) = ψrad (r)ψang (θ.4)
(6. θ. (6. r ˆ Hrad and ¸ ∙ Ze2 −~2 1 ∂ 2 ∂ r − = 2me r2 ∂r ∂r (4π 0 )r µ ∂ 1 ∂2 1 ∂ sin θ + sin θ ∂θ ∂θ sin2 θ ∂φ2 ¶ (6.3) ¶ µ 2 2 −Ze −~ ˆ 2 ψ ∇ + Eψ = 2me (4π 0 )ˆ r µ 2∙ ¶ µ ¶¸ −~ 1 ∂ 2 ∂ 1 ∂ 1 ∂2 1 ∂ −Ze2 Eψ = r + sin θ + ψ + 2me r2 ∂r ∂r r2 sin θ ∂θ ∂θ sin2 θ ∂φ2 (4π 0 )r The Hamiltonian is (almost) the sum of a radial part (only a function of r) and an angular part (only a function of θ and φ): 1 ˆ ˆ ˆ H = Hrad + 2 Hang . φ) = Eψang (θ.with the origin located on the nucleus. φ) It turns out that solving the Schrödinger equation. The classical potential energy for these hydrogenic systems is V (r) = So the Hamiltonian is −Ze2 .5)
−~2 ˆ Hang = 2me
(6.6)
Since the Hamiltonian is the sum of two terms. ψ(r. ˆ Hang ψang (θ. φ).8) (6.2)
Schrödinger’s equation (in spherical polar coordinates) becomes ˆ Eψ = Hψ (6.

φ) ¶ µ 1 ˆ ˆ Hrad + 2 Hang R(r)Ylm (θ. φ) = ER(r)Ylm (θ. φ) = 2me Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r). (Mathematica knows them and you can use them just like any other built-in function like sine or cosine.11) l(l + 1)~2 . φ)’s are the spherical harmonic functions characterized by quantum numbers l and m. φ) Hang ψang (θ. ˆ It also turns out that the energy associated with Hang is found to be E = El = So. The full Schrödinger equation becomes ˆ Hψ(r.13)
48
. The spherical harmonics are known functions. θ. (6.yields ψ ang (θ. φ) = Eψ(r.12) (6. φ) = ER(r)Ylm (θ.10)
(6. φ) H 2me r2 (6. r ˆ Operating with Hang we get ¶ µ 2 ˆ rad + l(l + 1)~ R(r)Ylm (θ. φ). φ) = ER(r)Ylm (θ. l(l + 1)~2 ˆ ψang (θ. φ) ˆ HR(r)Ylm (θ. φ). θ.) We shall use the spherical harmonics more next semester when we develop the quantum theory of angular momentum. φ) = Ylm (θ. 2me (6.9)
where the Ylm (θ.

The Ylm (θ.17)
Note: The energy levels are determined by n alone–l drops out. Anl . φ) can now be cancelled to leave a one dimensional diﬀerential equation: µ ¶ Ze2 l(l + 1) −~2 1 ∂ 2 ∂ r − − R(r) = ER(r). Discussion of the Wavefunctions
We are now very close to having the atomic orbitals familiar from freshman chemistry. n In fact. θ. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (6. (6. φ) (6. the total wavefunction that describes a hydrogenic system (ignoring the spin of the electron.e. So.
49
. i. the solutions to our diﬀerential equation are closely related to the Laguerre polynomials. (6.14) 2me r2 ∂r ∂r 4π 0 r r2 This diﬀerential equation is very similar to a known equation called Laguerre’s diﬀerential equation which has as solutions the Laguerre polynomials Ll (x).. the energy levels are given by En = − Z 2R n2 (6.18)
6. which will be brieﬂy discussed later) is ψ nlm (r. µ ¶l µ ¶ 2σ 2σ −σ/n 2l+1 Rnl (σ) = Anl .15) e Ln+1 n n
where the normalization constant. φ) = Rnl (r)Ylm (θ. Also Note: the energy levels are the same as for the Bohr model.2.16) na0 2n[(n + l)!]3 The energy eigenvalues.

We have explicitly derived the “physicists” picture of the atomic orbitals orbital n l 1s 2s 2p 3d 1 2 2 2 3 3 3 0 0 1 1 2 2 2 m 0 0 0 ±1 0 ±1 ±2 wavefunctions (σ = r/a0 ) ψ1s = ψ100 = e−σ ¡ ¢ ψ2s = ψ200 = 1 − σ e−σ/2 2 ψ2p0 = ψ210 = σe−σ/2 cos θ ψ2p±1 = ψ21±1 = σe−σ/2 sin θe±iφ ψ3d0 = ψ320 = σ2 e−σ/3 (3 cos2 θ − 1) ψ3d±1 = ψ32±1 = R32 (r) cos θ sin θe±iφ ψ3d±2 = ψ32±2 = R32 (r) sin2 θe±i2φ
The wavefunctions in the “physicists” picture are complex (they have real and imaginary components). ψ 2s . ψ 3d0 are pure real and so these are the same in the “chemists” picture as in the “physicists” picture. The atomic orbital you are used to from freshman chemistry are the “chemists” picture of atomic orbitals In the above table ψ1s . The table below lists the atomic orbitals in the “chemists” picture as linear combinations of the “physicists” picture wave functions. ψ 2p0 . The wavefunctions that chemists like are pure real. So one needs to form linear combinations of these orbitals such that these combinations are pure real.
50
.

electrons also posses an intrinsic quantity called spin. • ms is the spin orientation quantum number and ms = ±1/2 for electrons. Spin of the electron
ψ3dz2 = ψ3d0 £ ¤ 1 2 ±1 ψ3dxz = √2 ψ3d1 + ψ3d−1 £ ¤ 1 2 ±1 ψ3dyz = i√2 ψ3d1 − ψ3d−1 £ ¤ 1 2 ±2 ψ3dxy = √2 ψ3d2 + ψ3d−2 £ ¤ 1 ψ3dx2 −y2 = i√2 ψ3d2 − ψ3d−2
2 0
ψ1s = ψ1s ψ2s = ψ2s ψpz = ψ2p0 £ ¤ 1 ψ2px = √2 ψ2p1 + ψ2p−1 £ ¤ 1 1 ±1 ψ2py = i√2 ψ2p1 − ψ2p−1
As we know from freshman chemistry. so we can not write down an explicit function of the coordinate space variables. The spin wavefunction is a function in spin space not the usual coordinate space. For now we must be satisﬁed with the following: • There are two quantum numbers associated with spin: s and ms • s is the spin quantum number and for an electron s = 1/2 (always).orbital n l 1s 2s 2p 1 2 2 2 2 3d 3 3 3 3 0 0 1 1
m 0 0 0 ±1
wavefunctions (σ = r/a0 )
6.
51
. Spin is actually rather peculiar so we will put oﬀ a more detailed discussion until next semester.3.

Again note that for a free hydrogenic system the total energy depends only on the principle quantum number n.− 1 (the “spin-down” state)
2 2 2 2
6.3. can take on values of 1.2.4. n: determines the total energy of the systems and the atomic shells.19)
52
. • The angular momentum quantum numbers.ms and “tack it on” as another factor of the complete wavefunction. — The principle quantum number. When a particular spin state is needed a further notation is commonly used: α ≡ χ 1 . (6. l: determines the total angular momentum of the system. It also determines the atomic sub-shells (6.ms = Rnl (r)Yl. En = − The quantum numbers of the hydrogenic system • The principle quantum number.m (θ.ms = ψn.s.m χs. 1 (the “spin-up” state) and β ≡ χ 1 .20) n2 where recall.l. . φ)χ The energy is given by Z 2R . . Summary: the Complete Hydrogenic Wavefunction
We are now in position to fully describe all properties of hydrogenic systems (except for relativistic eﬀects) The full wave function is Ψn.m. n.We simply denote the spin wavefunction generally as χs.l.

± l. l = 3 is called f etc. . • The orientation quantum number. The Schrödinger theory is a non-relativistic one. m. spin-up or spin-down).— The angular momentum quantum number. l = 2 is called d.e. in the late 1920’s. — For electrons s = 1/2. This is not the full story however. it can not account for relativistic eﬀects which show up in spectral data. (n − 1) — For historical reasons l = 0 is called s. . • The spin orientation quantum number. We also had to add spin in an ad hoc manner to account for what we know experimentally–spin did not fall out of the theory naturally. . We have determined all that we can about the hydrogen atom within Schrödinger’s theory of quantum mechanics. developed a relativistic quantum theory in which the well established phenomenon of spin arose naturally. m: determine the projection of the angular momentum onto the z-axis. • The spin quantum number. can take on values of 0. . It also determines the orientation of the atomic sub-shells — The magnetic quantum number. can take on values of 0. that is. ms : determines the projection of the spin angular momentum onto the z-axis (i. ±1.. l = 1 is called p. 1. . . s: determines the total spin angular momentum. His theory also made the
53
. — For electrons ms = ±1/2 We have accomplished quite a bit. Dirac. l.

54
. The Dirac theory was still not fully complete. In 1948 Richard Feynman developed the beginnings of quantum electrodynamics (QED). so we limit ourselves to the non-relativistic Schrödinger theory. because there still existed experimental phenomena that was not properly described. Both the relativistic Dirac theory and QED are beyond our reach. QED is the best theory ever developed in terms of matching with experimental data.bold prediction of the existence anti-matter that has now been veriﬁed time and again.

In fact. helium. The problem must be solved by one of the following methods • Numerical solutions (we will not discuss this) 55
55
.7. Two Electron Atoms: Helium
We now consider a system consisting of two electrons and a nucleus.E of electron 1 P. It makes a closed form solution impossible.—elec.E of electron 2 P.1.E of electron 1 K. Although the extension from hydrogen to helium seems simple it is actually extremely complicated. (7. The Hamiltonian for helium is ~2 2 ˆ H= − ∇ 2me 1 | {z } ~2 2 − ∇ 2me 2 | {z } Ze2 − 4π r | {z 0 1 } Ze2 − + 4π 0 r2 | {z } e2 4π 0 r | {z 12 } . it is so complicated that it can’t be solved exactly. Multi-electron atoms
7.
The electron—electron repulsion term is responsible for the diﬃculty of the problem. The helium atom is an example of the “three-body-problem”–diﬃcult to handle even in classical mechanics–one can not get a closed form solution. for example. repulsion
where r12 = |r1 − r2 | is the distance between the electrons.E of eletcron 2
elec.1)
K.

1 and 2 must be exactly the same as when the electrons are labelled 2 and 1. photons): The total wavefunction for bosons must be symmetric under exchange of indistinguishable bosons. They can not truly be labelled. only |ψ|2 is directly measurable–not ψ itself.2) antisymmetric
The Pauli exclusion principle states: The total wavefunctions for fermions (e. say. The Pauli Exclusion Principle
Electron are fundamentally indistinguishable.• Perturbation theory (next semester) • Variational theory (next semester) • Ignore the electron—electron repulsion (good for qualitative work only)
7. ⎨ ψ(1. All this implies that ⎧ ⎪ +ψ(2. helium
56
. 1). 2) = or ⎪ ⎩ −ψ(2.. Now. Note: a similar statement exists for bosons (e. 1) symmetric (7.2.g. All physical properties of a system where we have labelled the electrons as. Let us consider the two electron atom.g.. electrons) must be antisymmetric under the exchange of indistinguishable fermions.

(7. However considering the symmetry with respect to exchange we see the following • Ψa has symmetric spatial and spin parts and is there for symmetric. we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions).3) Since a complete solution for helium is not possible we must use approximate wavefunctions. Now let’s blindly list all possibilities for the ground state wave function of helium Ψa = ψ1s (1)α(1)ψ1s (2)α(2) Ψb = ψ1s (1)α(1)ψ1s (2)β(2) Ψc = ψ1s (1)β(1)ψ1s (2)α(2) Ψd = ψ1s (1)β(1)ψ1s (2)β(2) These appear to be four reasonable ground state wavefunctions which would imply a four-fold degeneracy.The total wavefunction is Ψ = ψ(1. It must be excluded. • Ψb and Ψc have symmetric spatial parts. | {z }| {z }
spatial part spin part
(7. Ψ = ψ(1)ψ(2)χ(1)χ(2). one must make an antisymmetric linear combination of the spin parts. So. but the spin part is neither symmetric or antisymmetric.5)
57
.4)
where the single particle wavefunctions are that of the hydrogenic system. • Similarly for Ψd . 2)χ(1. 2) (7. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd. Since we are doing this. Likewise if the spatial part is odd then the spin part must be even.

3.7) (7.The appropriate linear combination is α(1)β(2) − α(2)β(1). . . . . ¯ ¯ . . . . ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s
58
. . . . The aufbau principle states that the ground state wavefunction is built-up of hydrogenic wavefunctions To arrive at an antisymmetric wavefunction we construct the Slater determinant: ¯ ¯ ¯ ψ (1)α(1) ψ1s (1)β(1) · · · ψn (1)α(1) ψn (1)β(1) ¯ ¯ 1s ¯ ¯ ¯ ¯ ψ1s (2)α(2) ψ1s (2)β(2) · · · ψn (2)α(2) ψn (2)β(2) ¯ ¯ Ψ=¯ (7. . .8) .6)
7. Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle. Many Electron Atoms
The remaining atoms on the periodic table are handled in a manner similar to helium. So the ground state wave function for helium is Ψg = ψ1s (1)ψ1s (2) [α(1)β(2) − α(2)β(1)] . The product wavefunction for the ground state is determined by applying the aufbau principle. Consequences of the Pauli exclusion principle • No two electrons can have the same ﬁve quantum numbers • Electrons occupying that same subshell must have opposite spins (7. .

The reason one can be sure that this wavefunction is the antisymmeterized is that we know from linear algebra that the determinant is antisymmetric under exchange of rows (corresponds to exchanging two electrons).11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1
59
. The Total Hamiltonian
The total Hamiltonian for a many electron (ignoring spin-orbit coupling which will be discussed next semester) atom is " # N X −~2 X e2 Ze2 ˆ ∇2 − + (7. Another property of the determinant is that if two rows are the same (corresponds to two electrons in the same state) the determinant is zero. This agrees with the Puli exclusion principle.3.1. and ψ2s α (or ψ 2s β). It is also antisymmetric under exchange of columns. ψ1s β.10)
• The short hand notation for these states is (1s)2 (2s)1 7. • We construct the Slater determinant as ¯ ¯ ¯ ψ (1)α(1) ψ (1)β(1) ψ (1)α(1) ¯ 1s 1s 2s ¯ ¯ ¯ ¯ Ψ1 = ¯ ψ1s (2)α(2) ψ1s (2)β(2) ψ2s (2)α(2) ¯ ¯ ¯ ¯ ψ (3)α(3) ψ (3)β(3) ψ (3)α(3) ¯ 1s 1s 2s or ¯ ¯ ¯ ψ (1)α(1) ψ (1)β(1) ψ (1)β(1) ¯ 1s 2s ¯ ¯ 1s ¯ ¯ Ψ2 = ¯ ψ1s (2)α(2) ψ1s (2)β(2) ψ2s (2)β(2) ¯ ¯ ¯ ¯ ψ (3)α(3) ψ (3)β(3) ψ (3)β(3) ¯ 1s 1s 2s
(7. As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α.9)
(7.

φ) which describe the position of the nuclei relative to the center of mass. This chapter will be limited to diatomic molecules. Molecular Energy
A diatomic molecule with n electrons requires that 3n+6 coordinates be speciﬁed.8.
60
60
. θ. we are able to begin the discussion of molecules. Diatomic Molecules and the Born Oppenheimer Approximation
Now that we have applied quantum mechanics to atoms. Three of these describe the center of mass position. R determines the internuclear separation and θ and φ determine the orientation.1. 3n of these describe the position of the n electrons.
8. This leaves three degrees of freedom (R.

The Hamiltonian In the center of mass coordinates the Hamiltonian for a diatomic molecule is ˆ ˆ ˆ ˆ ˆ ˆ H = TN + Te + VN N + VNe + Vee .
61
. ˆ TN is the nuclear kinetic energy operator and is given by
2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN ˆN = − ~ ∇2 = − ~ + J .1)
(8. R T 2μ 2μR2 ∂R ∂R 2μ
(8. +
ZB e2 4π 0 rBi
P ˆ VNe = − i P ˆ Vee = i>j
h
ZA e2 4π 0 rAi
i
is the nuclear—electron potential energy operator.1.
e2 4π 0 rji
is the electron—electron potential energy operator. P ~2 ˆ 2 ˆ Te = i − 2me ∇ei is the kinetic energy operator for the electrons.2)
m1 m2 m1 +m2
ˆ where J is angular momentum operator for molecular rotation and μ = the reduced mass of the diatomic molecule. ˆ VNN =
ZA ZBe e2 4π 0 R
is
is the nuclear—nuclear potential energy operator.1.8.

8.1.2. The Born—Oppenheimer Approximation The Born—Oppenheimer approximation: The nuclei move much slower than the electrons. (classical picture) We put the Born—Oppenheimer approximation to work by ﬁrst deﬁning an eﬀective Hamiltonian ˆ ˆ ˆ ˆ ˆ Hef f = Te + VN N + VNe + Vee . (8.3) The approximation comes in by treating R as a parameter rather than an operator (or variable). So one writes ˆ Hef f ψe (R, {ri }) = Ee (R)ψ e (R, {ri }). ψe is the so-called electronic wavefunction. Now the Schrödinger equation for the diatomic molecule is ³ ´ ˆ ˆ TN + Hef f ψ(R, {ri }) = Eψ(R, {ri }). (8.4)

(8.5)

Since the Hamiltonian is a sum of two terms, one can write the wavefunction ψ(R, {ri }) as a product wavefunction ψ = ψN ψe , (8.6)

where ψN is the so-called nuclear wavefunction. Substituting the product wavefunction into the Schrödinger equation gives ³ ´ ˆ ˆ (8.7) TN + Hef f ψN ψe = EψN ψe ³ ´ ˆ / / TN + Ee (R) ψ N ψe = EψN ψe ³ ´ ˆ TN + Ee (R) ψ N = EψN .

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The last equation is exactly like a Schrödinger equation with a potential equal to Ee (R). One now models Ee (R) or determines it experimentally.

8.2. Molecular Vibrations

As stated earlier R is the internuclear separation and θ and φ determine the orientation. Consequently, R is the variable involved with vibration whereas θ and φ are involved with rotation. Considering only the R part of the Hamiltonian (under the Born—Oppenheimer approximation), we have ∙ 2 2 ¸ ~ ∂ − + Ee (R) ψvib = Evib ψvib . (8.8) 2μ ∂R2 It is convenient at this point to expand Ee (R) in a Taylor series about the equilibrium position, Req : ¶ µ ¶ µ ∂E 1 ∂2E 0 (R − Req ) + (R − Req )2 + · · · . (8.9) Ee (R) = E + 2 ∂R Req 2! ∂R Req Now E 0 is just a constant which, by choice of the zero of energy, can be set to an arbitrary value. Since we are at a minimum, One deﬁnes ³

∂2E ∂R2

´

¡ ∂E ¢

∂R Req

must be zero, so the linear term vanishes.

Req

≡ ke as the force constant.

The remaining terms in the expansion can collective be deﬁned as O[(R−Req )3 ] ≡ Vanh , the anharmonic potential.

63

As a ﬁrst approximation we can neglect the anharmonicity. With this, the Schrödinger equation becomes ∙ 2 2 ¸ ~ ∂ 1 2 − + ke (R − Req ) ψvib = Evib ψvib . (8.10) 2μ ∂R2 2 If we let x = (R − Req ) this becomes ¸ ∙ 2 2 1 ~ ∂ 2 + ke x ψvib = Evib ψvib , − 2μ ∂x2 2 which is exactly the harmonic oscillator equation. Hence √ 2 ψ vib,n = An Hn ( αx)e−αx /2 , where α ≡ And q q

ke μ . ~

(8.11)

(8.12)

1 Evib,n = hc˜ e (n + ), ω 2

ke . μ

(8.13)

where ω e ≡ ˜

1 2π

8.2.1. The Morse Oscillator Neglecting anharmonicity and using the harmonic oscillator approximation works well for low energies. However, it is a poor model for high energies. For high energies we need a more realistic potential–one that will allow of bond dissociation. The Morse potential Ee (R) = De [1 − e−β(R−Re q ) ]2 , (8.14)

64

μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. Note: ω this expression for the Morse potential has the zero of energy at the bottom of the well (i.e. R = Req , ;Ee (Req ) = 0).

q

The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Re q ) ]. (8.15)

Now the zero of energy is the dissociated state (i.e. R → ∞, ;Ee (R → ∞) = 0). We approach this quantum mechanical problem exactly like all the other. The Schrödinger equation is ¸ ∙ 2 2 ~ ∂ −β(R−Req ) 2 + De [1 − e ] ψvib = Evib ψvib − 2μ ∂R2

(8.16)

This is another diﬀerential equation that is diﬃcult to solve.

As it turns out, this Schrödinger equation can be transformed into a one of a broad class of known diﬀerential equations called conﬂuent hypergeometric equations– the solutions of which are the conﬂuent hypergeometric functions, 1 F1 . Doing this yields the wavefunctions of the form ψvib,n (z) = z Apn e−z 1 F1 (−n, 1 + 2Apn , 2z), √ 2De μ −βx e , z = βh √ 2μ , A = βh p −1 − n pn = De + 2 A and energy levels of the form 1 1 Evib,n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 , ω ω 2 2 (8.17)

(8.18)

65

where ω e xe together is the anharmonicity constant, with xe = ˜ ∗ ∗ ∗ See Handout ∗ ∗∗ 8.2.2. Vibrational Spectroscopy

hc˜ e ω . 4De

Infrared (IR) and Raman spectroscopy are the two most widely used techniques to probe vibrational levels. The spectral peaks appear at v = ˜

4E hc

(in units of wavenumbers, cm−1 ).

The transition from the n = 0 to the n = 1 state is called the fundamental transition. Transitions from n = 0 to n = 2, 3, 4 · · · are called overtone transitions. Transitions from n = 1 to 2, 3, 4 · · · , n = 2 to 3, 4, 5 · · · , etc. are called hot transitions (or hot bands) Since the energy levels depend on mass, isotopes will have a diﬀerent transition energy and hence appear in a diﬀerent place in the spectrum. Heavier isotopes have lower transition energies.

66

**9. Molecular Orbital Theory and Symmetry
**

9.1. Molecular Orbital Theory

One of the most important concepts in all of chemistry is the chemical bond. In freshman chemistry we learn of one model for chemical bonding–VSEPR (valence shell electron-pair repulsion) theory, where hybridized atomic orbitals determine the bonding geometry of a given molecule. We are now prepared to discuss a bonding theory that is more rigorously based in quantum mechanics. Basically we will treat the molecules in the same way as all our other quantum mechanical problems (e.g., particle in a box, harmonic oscillator, etc.) As you might expect, it is not possible to obtain the exact wavefunctions and energy levels so, we must settle for approximate solutions. As a ﬁrst example, let us consider the molecular hydrogen ion H+ . 2 The Hamiltonianfor H+ is 2 ˆ ˆ ˆ ˆ ˆ H = TN + Tel + VNel + VNN 67

67

(9.1)

We use the Born-Oppenheimer approximation and treat the nuclear coordinates as a parameters rather than as variables. So we only worry about parts of the Hamiltonian that deal with the electron. The eﬀective Hamiltonian becomes ˆ ˆ ˆ H = Tel + VNel e2 e2 −~2 2 ∇ − − . = 2me 4π 0 rA 4π 0 rB The eigenfunctions of this Hamiltonian are called molecular orbitals. The molecular orbitals are the analogues of the atomic orbitals. • Atomic orbitals: Hydrogen is the prototype and all other atomic orbitals are built from the hydrogen atomic orbitals. • Molecular orbitals: The hydrogen molecular ion is the prototype and all other molecular orbitals are built from the hydrogen molecular ion molecular orbitals. (9.2)

There is one signiﬁcant diﬀerence between the above, which is the hydrogen atomic orbitals are exact whereas the hydrogen molecular ion molecular orbitals are not exact. In fact, we shall see that these molecular orbitals are constructed as linear combinations of atomic orbitals.

9.2. Symmetry

Let the atoms of the hydrogen molecular ion lie on the z-axis of the center of mass coordinate system.

68

3)
Cylindrical symmetry
69
. • The above symmetry therefore requires that the molecular orbitals be eigenfunctions of the inversion operator. (9.Inversion symmetry • The potential ﬁeld of the hydrogen molecular ion is cylindrically symmetric about the z-axis. −z) = aψ(x. −z). • If a = +1 the molecular wavefunction is even with respect to inversion and is called gerade and labelled with a “g”: ˆψ g = ψg ı • If a = −1 the molecular wavefunction is odd with respect to inversion and is called ungerade and labelled with a “u”: ˆψ u = −ψu ı • The terms gerade and ungerade apply only to systems that posses inversion symmetry. y. y. y. That is ı ˆψ(x. • Because of the symmetry the electron density at (x. ı • Moreover the eigenvalue a can be either +1 or −1. −y. z). z) must equal the electron density at (−x. ˆ. z) = ψ(−x. −y.

— We use λ to label the molecular orbitals as shown in the table λ 0 label σ ±1 ±2 · · · π δ ···
Mirror plane symmetry
70
. . . • The molecular wavefunction is described by an eigenvalue λ = 0. ±2.• The cylindrical symmetry implies that the potential energy can not depend on the φ. ±1. .

• There is also a symmetry about the x-y plane called horizontal mirror plane symmetry: operator σ h .
71
. ˆ • Thus the molecular wavefunction must be an eigenfunction of σ h with eigenˆ value ±1. — If the eigenvalue is −1 (odd with respect to σ h ) the molecular orbital ˆ is called an antibonding orbital. • There are also vertical mirror plane symmetries. but we will put that discussion oﬀ for the time being. — If the eigenvalue is +1 (even with respect to σ h ) the molecular orbital ˆ is called a bonding orbital.

1) and (1sB ) = ke−rB /a0 (10. we need to ﬁnd some useful approximations for them. Let us again consider the hydrogen molecular ion H+ : let one H atom be labelled 2 A and the other labelled B. LCAO is qualitatively very useful but it lacks quantitative precision. Linear combination of the 1s atomic orbital from each H atom is used for the molecular orbital of H+ : 2 (1sA ) = ke−rA /a0 (10. Useful can mean qualitatively useful or quantitatively useful.10.2)
72
72
. Molecular Orbital Diagrams
10.1. Unfortunately we can’t have both. LCAO–Linear Combinations of Atomic Orbitals
Now that we know what symmetry the molecular orbitals must posses. We will discuss the approximation which models the molecular orbitals as linear combinations of atomic orbitals (LCAO).

Classiﬁcation of Molecular Orbitals With atoms we classiﬁed atomic orbitals according to angular momentum.5)
As can be seen from the above ﬁgure.We construct two molecular orbitals as Φ+ = C+ (1sA + 1sB ) and Φ− = C− (1sA − 1sB ) The normalization condition is Z Φ± Φ± dΩ = 1 (10. Φ+ represents a situation in which the electron density is concentrated between the nuclei and thus represents a bonding orbital.1.3)
(10.
73
.1. For molecular orbitals we shall also classify them according to angular momentum. But we shall also classify them according to their inversion symmetry and wether or not they are bonding or antibonding.4) (10. Conversely Φ− represents a situation in which the electron density is very low between the nuclei and thus represents an antibonding orbital 10.

The classiﬁcation according to angular momentum is as follows.. The classiﬁcation according to bonding or antibonding is an asterisk is used to denote antibonding. pz ⇒ σ. For example.g. This molecules is a homonuclear diatomic with two electrons. e. For example. The classiﬁcation according to inversion symmetry is simply a subscript “g” or “u”. If the two atoms are inﬁnitely far apart.
10. Those with m = ±1 form π type molecular orbitals. The ground state of the system would consist of two separate hydrogen molecules in their ground atomic states: (1s)1
74
.2. The Hydrogen Molecule
Let us now consider the hydrogen molecule.. e. s ⇒ σ. σ g is a bonding orbital and σ ∗ is an antibonding u orbital. λ 0 orbital symbol σ ±1 ±2 · · · π δ ···
Atomic orbitals with m = 0 form σ type molecular orbitals. px ⇒ π etc.g. σ g or σ u etc.

As the atom are brought closer together. These are σg = 1sA + 1sB and σ ∗ = 1sA − 1sB .6)
75
. There are two acceptable linear combinations. u (10. their respective s orbitals begin to overlap.
It is now more appropriate to speak in terms of molecular orbitals.7) (10. so one forms linear combinations of the atomic orbitals.

10.It can be shown mathematically that the energy level associated with σg is lower than σ∗ . Molecular Orbital Diagrams
The energy levels associated with the molecular orbitals are drawn schematically is what is called a molecular orbital diagram. u We can intuit this qualitatively however since the σ ∗ orbital must have a node u whereas the σ g does not.3.
76
. Some get very complicated. The molecular orbital diagram for H2 is shown below
Molecular orbital diagrams can be drawn for any molecule. We will focus on the second row homonuclear diatomics and some simple heteronuclear diatomics. It is also to be expected since we know H2 is a stable molecule.

Bond order • One important property that can be predicted from the molecular orbital diagrams is bond order. ∗ ∗ ∗ See Supplement ∗ ∗∗ The supplement that follows this section contains examples for each of the second row diatomics. A consequence of this energy level disparity is that molecular orbitals may be formed from nonidentical atomic orbitals.
77
. • Bond order is deﬁned as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (10. For example a high lying 1s orbital may combine with a low lying 2s orbital to form a σ molecular orbital. This disparity is not present for homonuclear diatomics. Heteronuclear diatomics are some what more complicated since there is a disparity in the energy levels of the atomic orbitals for the separated atoms. The supplement that follows this section contains some examples of heteronuclear diatomics.8)
• Examples follow in the supplement.The molecular orbital diagrams for the second row homonuclear diatomics are rather simple.

10. Likewise we have discussed molecular orbitals which are the electronic wavefunctions. (Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10.4.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot
78
. The Complete Molecular Hamiltonian and Wavefunction
We have discussed molecular vibrations which under the Born-Oppenheimer approximation are governed by the vibrational Hamiltonian and described by the vibrational wavefunction. Next semester we will discuss molecular rotations and just like for vibrations and electronic transitions they are governed by the rotational Hamiltonian and described by the rotational wavefunction. We can succinctly express the Schrödinger equation for a molecule as follows.

79
79
. (11. we have to take several key results from that theory on faith. When the light interacts with the molecule an electric dipole is induced according to μ = αE.1) where α is the polarizability of the molecule describing the “ﬂexibility” of its electron cloud. An Aside: Light Scattering–Why the Sky is Blue
This chapter addresses the topic of light scattering from two diﬀerent perspectives.11. • Classical electrodynamics • Classical statistical mechanics Since this is not a course on electrodynamics.
11. The Classical Electrodynamics Treatment of Light Scattering
As usual we work under the electric dipole approximation and only focus on the interaction of the electric ﬁeld part of light with a dipole.1.

80
. The second term corresponds to Stokes Raman scattering where the scattered light is shifted to the red of the incident frequency. ω − ωv and ω + ω v as part of three terms in the above expression. In this case we see the dipole oscillates at three distinct frequencies: ω.For light. Thus the light—matter interaction is described as μ(t) = α(t)E(t) = (α0 + α1 cos ω v t) E0 cos ωt = α0 E0 cos ωt + α1 E0 cos ω v t cos ωt ⎡ ⎤ α1 E0 ⎣ cos(ω − ω v )t + cos(ω + ω v )t ⎦ = α0 E0 cos ωt + | {z } {z } | {z } | 2
Rayleigh Stokes Raman AntiStokes Raman
(11. (11.
According to classical electrodynamics an oscillating dipole emits an electromagnetic ﬁeld at the oscillation frequency. The ﬁrst term corresponds to Rayleigh scattering where the scattered light is at the same frequency as the incident light. That is. the electric ﬁeld part is E(t) = E0 cos ωt. there is a vibrational (and rotational) contribution to the polarizability: α(t) = α0 + α1 cos ωv t (here for simplicity we assume only one vibrational mode).2)
The polarizability also depends on the positions of nuclei to some degree.4)
where a trig identity was used in the last step.3)
(11.

It can be shown that the emitted intensity is I= ω4 2 μ.2. 3c3 0 (11.5)
where μ0 = α0 E0 for the case of Rayleigh scattering and μ0 = α1 E0 /2 for the case of Raman scattering. in fact.The third term corresponds to anti-Stokes Raman scattering where the scattered light is shifted to the blue of the incident frequency.
81
. the reason why the sky is blue (from the point of view of classical electrodynamics) and is called the Rayleigh scattering law.
11. There is a very strong dependence on frequency (or wavelength). This quartic scattering dependence is. Classical electrodynamics can describe exactly how the oscillating electric dipole emits electromagnetic radiation. The important point to note is that I ∝ ω 4 or alternatively I ∝ 1/λ4 . The Blue Sky
The spectrum of visible light from the sun incident on the outer atmosphere is essentially ﬂat as shown below. To explicitly derive this expression we would need a fair bit of electrodynamics and so the derivation is not shown here.

but red sunsets occur for the same reason– Rayleigh scattering. 11.
82
. Sunsets We have focused on a blue sky.2.1.
The following ﬁgures illustrate why Rayleigh scattering implies that the sky is blue.We just learned that light scatters as it traverses the atmosphere according to Rayleigh’s scattering law: I(λ) ∝ 1/λ4 .

11.
83
. White Clouds We might expect that clouds should be highly colored since they consist of droplets of water which scatter light very eﬀectively.2. This more pronounced at dawn or dusk since the light must traverse more of the atmosphere at those times then at noonday at which time the sun appears yellow in color.If we look directly at the sun during a sunset (or sunrise) it appears red because most of the blue light has scattered in other directions.2.

Mie scattering is referred to as Tyndall scattering
84
. In this limit an entirely diﬀerent analysis is made–one does not have Rayleigh scattering but instead has a process called Mie scattering. particularly in liquid suspensions. The water droplets are much larger than the wavelenght of the light–quite the opposite case as above. In some contexts.The key diﬀerence between light scattering by clouds versus by the atmosphere is the size of the scatterer.

θ. φ) • The radial part is.6)
µ
2σ n
¶l
e
−σ/n
2l+1 Ln+1
µ
2σ n
¶
. Anl .7)
where the normalization constant. φ) = Rnl (r)Ylm (θ. This section should not substitute for your studying of the rest of this material.
Equations
• The wavefunctions for the hydrogenic system are ψnlm (r. The equations are collected here simply for handy reference for you while working the problem sets.Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. Rnl (σ) = Anl (11.8) na0 2n[(n + l)!]3 85
85
. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.
(11. depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.

R → ∞. (11. • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib.e. 2 n n! π ~ 2
(11. An = p √ . 2 2 where ω e xe together is the anharmonicity constant.11)
Ee (R) = De [1 − e−β(R−Re q ) ]2 . . • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ]. .e.n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 . ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i.
• The energy levels are 1 En = (n + )~ω. 4De
(11. ω = 2 • The Morse potential is
r
k m
(11.14)
86
. y = x. (11. with xe = ˜
hc˜ e ω .Ee (Req ) = 0).13)
Now the zero of energy is the dissociated state (i.• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11. R = Req .12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter.10)
where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.Ee (R → ∞) = 0).9)
• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e .

• Bond order is deﬁned as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (11.15)
• The Rayleigh scattering law is I(λ) ∝ 1/λ4 ∝ ω 4 (11.16)
87
.

Part III Statistical Mechanics and The Laws of Thermodynamics
88
88
.

which allows one to handle macroscopic sized systems without losing to much of the rigor.
89
89
. Statistics and Entropy
Probability and statistics is at the heart of statistical mechanics. We will need some deﬁnitions • Ensemble: A large collection of equivalent macroscopic systems. but often Avogadro’s number of molecules. It is simply impossible.
12. we use a very detailed theory.1. to write down and solve the Schrödinger equation for those 100 million molecules. Rudiments of Statistical Mechanics
When we study simple systems like a single molecule. say. quantum mechanics.12. So we need a less detailed theory called statistical mechanics. The systems are the same except that each one is in a diﬀerent so-called microstate. even with the fastest computers. most of the time in the real world we are dealing with macroscopic systems. However. at least 100 million molecules.

Boltzmann developed an equation to connect the microscopic properties of an ensemble to the macroscopic properties. outcome 1 after N measurements. One valuable piece of statistical information about system is knowing how many diﬀerent ways the system appears p times in.3)
90
. p) is also called the binomial coeﬃcient because it gives the coeﬃcient for the pth order term in the expansion (1 + x) =
N N X p=0
C(N.1. p) = N! . say.
(12. This is given by the mathematical formula for combinations C(N. p!(N − p)! (12..1)
The number C(N. ﬂipping coins).• Microstate: The single particular state of one member of the ensemble given by listing the individual states of each of the microscopic systems in the macroscopic state. • Conﬁguration: The collection of all equivalent microstates. The number of possible conﬁgurations is deﬁned as W.g.2) (12. 12. p)xp . Combinations and Permutations Consider a random system that when measured can appear in one of two outcomes (e.1. The Boltzmann equation is S = k ln W Where S is entropy and k is Boltzmann’s constant.

p) = 1 1 N! C(N. Set x = 1 in the above.This formula will allow us to derive a normalization constant so that we can obtain the probability of obtaining p measurements of state 1.4)
2N =
C(N. p). This gives (1 + 1)
N
=
N X p=0 N X p=0
C(N.6)
where N is the total number of measurements and Ni is the number of indistinguishable results of type i. Sometimes the order is important. p) = N N 2 2 p!(N − p)! (12. ∗ ∗ ∗ See Examples on Handout ∗ ∗∗ For both combinations and permutations we need to evaluated factorials.
91
. So rather than a particular combination.
So the probability of any one outcome of N measurements is P (N. p)(1)p
(12. {Ni }) = N! N1 !N2 !N3 ! · · · (12. This is given by W (N.5)
For combinations we did not care what order the results of the measurements occurred. we are interested in a particular permutation.

The ﬂuctuation about an average value for any observable property O is described by the variance which is deﬁned as ¯ σ 2 ≡ O2 − O2 . but when we consider macroscopic systems (1020 or so molecules) no calculator can handle factorials of such large numbers. Consequently.9)
1 √ N
= 10−12
92
. the value of a certain property ﬂuctuates about the average value. Macroscopic equilibrium is a dynamic rather than static equilibrium. • Sterling’s approximation is ln(N!) ' N ln N − N (12. It can be shown that (12. but sometimes it is important. So for example if N = 1024 then
(12. Fluctuations
When we list the macroscopic properties of a material such as a beaker of benzene or the air of the atmosphere.2.This is no problem for small numbers. ¯ O N where N is the number of particles. Sterlings Approximation: • In place of evaluating factorials of large number one can use Sterling’s approximation to approximate the value of the factorial.7)
12.8)
σO 1 ≈√ . we speak of the average value of the property. O σ O is consider the range of the observable property. Often this ﬂuctuation is not important.

93
.For ensembles having large numbers of particles measured values of a property are extremely sharply peaked about the average value.

E. 94
94
. N= X
i
X
i
Ni i .
(13.13. of course. The total number of particles is. and the total number of particles will be constant. The Boltzmann Distribution
Consider a isolated system of N molecules that has the set { i } energy levels associated with it. Since the system is isolated the total energy.2)
The number of conﬁgurations for the system is then given by the number of distinct permutations of the system W = N! . The total energy is given by E=
where Ni is the number of particles in energy state i. N1 !N2 ! · · · (13.3)
A system in equilibrium always tries to maximize entropy and minimize energy and so the equilibrium conﬁguration is a compromise between these two cases.1)
Ni
(13.

Minimizing energy would be the case where all the particles are in the ground state (say 1 ). The derivation using Lagrange multipliers arrives at the conﬁguration in which the gi e−β i Ni = N P . We will not discuss this method in detail and consequently we cannot derive the equilibrium conﬁguration.4) −β j j gj e | {z }
pi
where β ≡
1 kT
and gj denotes the degeneracy of states having energy
j. (13. We start by considering our original system–that being one with constant energy. That is all Ni = 1 or 0. These two situations are contradictory and some compromise must be obtained.
95
. Maximizing entropy corresponds to maximizing W (via S = k ln W ).For the moment let us relax the isolation constraint. This is done using the mathematical technique of Lagrange multipliers (page 951 of your calc book). This would be the situation in which every particle was in a diﬀerent energy state. E and number of particles N To determine the equilibrium conﬁguration we must ﬁnd the maximum W subject to the constraint of constant energy and constant number of particles.

The analysis readily generalizes to variable energy i.
96
.The pi represents the probability of ﬁnding the a randomly chosen particle or system which has energy i .. β and hence T are constants.1. A given energy E will correspond to a unique temperature T. nonisolated systems by considering T as a variable.5)
j
Since we started with a isolated system.
13.6)
and is called the canonical partition function.e. Partition Functions
We have already come across both the partition functions that we will use in this class. The ﬁrst is W –the number of conﬁgurations. This is called the microcanonical partition function. This is the Boltzmann distribution gi e−β i Pi = P −β j gj e (13. This partition function is not very useful to us so we will not discuss it further. The second partition function is Q= X
j
gj e−βEj
(13.

1. That is. but it is a very good approximation for large numbers of particles. In the following we give an argument which provides a relation between the partition functions. But this an inconvenient connection because. (Note: the symbol Z is also often used for the canonical partition function.1. It is not an exact relation as we derive it.
97
. In fact we have already seen this in the S = k ln W. Relation between the Q and W When we get to connecting quantum mechanics with thermodynamics it will prove convenient to use Boltzmann’s equation (S = k ln W ) but as was stated earlier it is not convenient to use the microcanonical partition function (W ). for among other reasons.This was ﬁrst encountered as the denominator of the Boltzmann distribution and it is extremely important in statistical mechanics. We shall see in the next chapter that the partition function will provide a link between the microscopic (quantum mechanics or classical mechanics) and the macroscopic (thermodynamics). There are other partition functions that are useful in diﬀerent situations but we will do nothing more than list two important ones here: i) the grand canonical partition function and ii) the isothermal—isobaric partition function 13. the partition function contains all that can be known about the ensemble. energy levels and temperature do not explicitly appear.) The partition function is to statistical mechanics as the wavefunction is to quantum mechanics.

The microcanonical partition function describes a system at ﬁxed energy E. In fact W is the number of available states of the ensemble at the particular energy E. This is essentially the same as the degeneracy of the ensemble gE . Conversely the canonical partition function describes a system with variable energy. However, based on our previous discussion of ﬂuctuations, even though the energy of the ensemble is allowed to vary, the number of states with energy equal to the ¯ average energy E is overwhelmingly large. That is, almost every state available ¯ to the ensemble has energy E. We can express these ideas mathematically to come up with a relation between W and Q. The canonical partition function is Q= but to a good approximation Q ' gE e−β E . ¯

¯

X

j

gj e−β j ,

(13.7)

(13.8)

Now since the degeneracy is essentially the microcanonical partition function we have ¯ (13.9) Q ' W e−β E . So the canonical partition function is a Boltzmann weighted version of the microcanonical partition function. We will soon make use of the Boltmann’s equation in terms of the canonical

98

**partition function: ln Q ' ln(W e−β E ) = ln W + ln(e−β E ) ¯ E = ln W − | {z } kT .
**

S/k ¯ ¯

(13.10)

so,

S = k ln Q +

¯ E T

(13.11)

**13.2. The Molecular Partition Function
**

We ended the previous chapter by stating the total molecular energy (about the center of mass) as = ele + vib + rot . (13.12) This is a consequence of the Born Oppenheimer approximation If we include the center of mass translational motion this is = The ith total energy level is

i ele

+

vib

+

rot

+

trans

(13.13)

=

ele,n

+

vib,v

+

rot,J

+

trans,m .

(13.14)

Now if we have a collection of molecules in a macroscopic system. A given conﬁguration (say, conﬁguration j) of that system has total energy Ej . So the canonical partition function is Q= X

j

gj e−βEj

(13.15)

99

**But, each Ej is made up of the contributions of all of the molecules: Ej =
**

a l

+

b m

+

c n

+ ···

(13.16)

**The partition function for the molecule is written as Q = = X
**

j

**gj e−βEj = gla e−β {z
**

a l

X |l

qm o l,a

where the qmol,i are the molecular partition functions.

}|m

X

l,m,n···

a gm e−β qm o l,b

X {z

**b c (gla gm gn · · · )e−β( l + m + n +··· )
**

a m

a

b

c

(13.17)

}| n {z

X

a gn e−β n · · ·

a

qm o l,c

}

The total canonical partition function is the product of the molecular partition functions. For the case where the molecules are the same then all the qmol,i are the same: qmol,i = qmol thus qN (13.18) Q = mol . N! This allows us to focus only on a single molecule: qmol = X

i

**gi e−β i = gele,n e−β
**

qele

X |n

n,v,J,m

ele ,n

X }| v

n s,m ) gele,n gvib,v grot,J gtrans,m e−β ( ele,n + v ib ,v + ro t,J + tra(13.19)

{z

X

gvib,v e−β

qv ib

v ib ,v

{z

}| J

X

grot,J e−β

qro t

ro t,J

{z

}|m

X

gtrans,m e−β

qtra n s

tra n s,m

{z

}

We now collect below the expression for each of these partition functions. You will get the chance to derive each of these for your home work

100

The Translational Partition Function qtrans = where V Λ3 (13.20)

h Λ≡ √ 2πmkT is the thermal de Broglie wavelength. The Rotational Partition Function (linear molecules)

(13.21)

We will discuss rotations next semester. However, the high temperature limit, which works for all gases (of linear molecules) except H2 is T (13.22) qrot ≈ σθr

h where θr ≡ 8π2 Ik (I is the moment of inertia) and σ is the so-called symmetry number in which σ = 1 for unsymmetrical molecules and σ = 2 for symmetrical molecules.

2

**The Vibrational Partition Function qvib e− 2 β~ω 1 = = −β~ω 1−e 2 sinh 1 β~ω 2
**

1

(13.23)

Note this is for the harmonic oscillator. At temperatures well below the dissociation energy this is a very good approximation. (You will derive this as a homework problem.) The Electronic Partition Function There is usually only a very few electronic states of interest. Only at exceedingly high temperatures does any state other that the ground state(s) become important

101

so qele =

X

i

gele,i e−β

tele ,i

≈ gele,ground

(13.24)

102

14. Statistical Thermodynamics

The partition function allows one to calculate ensemble averages which correspond to macroscopically measurable properties such as internal energy, free energy, entropy etc. In this chapter we will obtain expressions for internal energy, U, pressure, P, entropy, S, and Helmholtz free energy, A. With these quantities in hand we will, in the subsequent chapters, formally develop thermodynamics with no need to refer back to the partition function. Ensemble averages The ensemble average of any property is given by 1 X ¯ O= Oi gi e−β i . Q i Internal energy One critical property of an ensemble is the average (internal) energy U. 1 X −β i ¯ . U ≡E= i gi e Q i Let us look closer at the above expression. Recall that Q= X

i

(14.1)

(14.2)

gi e−β i .

(14.3)

103

103

**Now take the derivative of Q with respect to β gives Ã #! " ¶ µ X µ ∂e−β i ¶ ∂ X −β i ∂Q = gi e = gi ∂β n,V ∂β i ∂β n,V i n,V X = − gi i e−β i
**

i

(14.4)

**By comparing this to the expression for U, we see µ ¶ ¶ µ 1 ∂Q ∂ ln Q U =− =− , Q ∂β n,V ∂β n,V where we used the identity
**

1 ∂y y ∂x

(14.5)

=

∂ ln y . ∂x

Pressure Another important property is pressure. When the ensemble is in the particular state i, d temperature and number of particles ¶ µ ∂ i pi = − ∂V n,β

i

= −pi dV . So at constant (14.6)

Thus the ensemble average pressure is given by ¶ µ 1 X ∂ i P =p=− ¯ gi e−β i . Q i ∂V n,β Multiplying by β/β we get 1 X P =− gi βQ i Using the chain rule in reverse, i.e., ∂e−β ∂V z }| ¶ µ ¶ µ ¶ µ −β i { ∂ i ∂e ∂ i = =− βe−β ∂ i ∂V ∂V

−βe−β

i

(14.7)

µ

∂ i ∂V

¶

βe−β i .

(14.8)

n,β

i

i

(14.9)

104

It is S = U + k ln Q T µ ¶ ∂ ln Q = −kβ + k ln Q ∂β n.V (14. βQ ∂V n.β n.11) (14.10)
105
.β Entropy We have already obtained the expression for entropy.we proceed as ! Ã µ −β i ¶ ∂e 1 1 X ∂ X −β i P = gi = gi e βQ i ∂V βQ ∂V i n.β β ∂V n.β µ ¶ µ ¶ ∂Q 1 1 ∂ ln Q = = .

We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well. it is the energy of the system minus the energy that is “tied-up” in the random (unusable) thermal motion of the particle in the system: A ≡ U − T S Free energy is probably the key concept in thermodynamics and so we will discuss it in much greater detail later. The Helmholtz free energy has the most direct relation to the partition function as can be seen from µ ¶ ¶ µ ∂ ln Q ∂ ln Q A ≡ U − TS = − + kT β − kT ln Q (14.Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work.12) ∂β ∂β n.V = −kT ln Q Any thermodynamic property can now be obtained from the above functions as we shall see in the following chapters. That is.V n.
106
.

1. Summary of Relations 1. ∗ ∗ ∗ See Handout ∗ ∗∗ 15. Properties of Partial Derivatives
Of critical importance in mastering thermodynamics is to become proﬁcient with partial derivatives.
15. y): µ ¶ µ ¶ ∂z ∂z dz = dx + dy ∂x y ∂y x 2.2)
. The chain rule for partial derivatives: µ ¶ µ ¶ µ ¶ ∂u ∂z ∂z = ∂x y ∂u y ∂x y 107
107
(15.1)
(15.1. Thermodynamics is a theory describing the most general properties of macroscopic systems at equilibrium and the process of transferring between equilibrium states. The total derivative of z(x.1. Thermodynamics is completely independent of the microscopic structure of the system.15. Work
We now begin the study of thermodynamics.

4) ¶
z
5. Environment: Everything not included in the system (or set of systems) Note that the distinction between the system and the environment is arbitrary and is chosen as a matter of convenience. The reciprocal rule:
µ µ ∂z ∂x
∂z ∂x
¶ µ
y
∂x ∂z
¶
=1 ¶
(15.3. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment. Deﬁnitions
System: a collection of particles Macroscopic systems: Systems containing a large number of particles. Closed system: A system that cannot exchange matter with its environment but may exchange energy. The cyclic rule:
¶
y
∂z =− ∂y ∂z ∂x ¶
µ
¶ µ
x
∂y ∂x
(15. 15. Microscopic systems: Systems containing a small number of particles.2.2.5)
u
15.
108
.1.3)
y
4. Finally
µ
∂z ∂x
¶
=
u
µ
+
y
µ
∂z ∂y
¶ µ
x
∂y ∂x
(15.

volume moles
= molar volume. mass. Extensive properties can be “converted” to intensive properties through ratios: Extensive property → Intensive property. Extensive property For example
mass volume
(15.2. • Work is exchanged if external parameters are changed during the process.3. 15. • For example. • Heat is exchanged if only internal parameters are changed during the process. volume. heat capacity. Adiabatic system: A closed system that also can not exchange heat energy with its environment. Work and Heat
A system may exchange energy with its environment or another system in the form of work or heat. temperature.
109
. System Parameters
Extensive parameters (or properties): properties that depend on the amount of matter. • For example.
heat capacity mass
15. pressure.6) = speciﬁc heat.Open system: A system that may exchange matter and energy with its environment. Intensive parameters (or properties): properties that are independent of the amount of matter. density.2.
= density.

g.g. is positive (w > 0) if work is done on the system. Heat.Convention Work. or more generally as dw = X
i
(15.3. Heat is negative (q < 0) if heat is released from the system. q. which acts as ‘generalized displacement. 15.1. Joules). meters). Newtons) and the generalized displacement need not have units of position (e. w.7)
For thermodynamics. times and inﬁnitesimal change in position. Work is negative (w < 0) if work is done by the system.’ Note that the generalized force need not have units of force (e. but the product of the two must have units of energy (e. Generalized Forces and Displacements In physics you learned that an inﬁnitesimal change in work is given by the product of force. a.g.8)
Ai dai
(15. The inﬁnitesimal amount of work done on the system is then given by dw = Ada.. F ..9)
110
. (15. we need a more general deﬁnition if inﬁnitesimal work. Any given external parameter. is positive (q > 0) if heat is absorbed by the system. A may be considered as a ‘generalized force’ which is coupled to a particular internal parameter.. dx: dw = F dx.

dn Height. dA Charge. dV Strain.3. μ Gravity.if more than one set of parameters change. a Contribution to dw Pressure.10)
Expanding Gases Consider the work done by a gas expanding in piston from volume V1 to V2 against some constant external pressure P = Pex (see ﬁgure)
111
. H Chemical Potential. E Magnetic Field. dh −P dV σdε γdA EdQ HdM μdn mgdh
15. That is dw = −P dV.2. γ Voltage. A Generalized Displacement. this is called P V work. −P Stress. dQ Magnetization. mg Volume. dM Moles. The following table gives some examples of generalized forces and displacements Generalized Force. (15. dε Surface area. σ Surface tension. P V work In principle all work is interchangeable so that without loss of generality we will develop the formal aspects of thermodynamics assuming all work is due to changes in volume under a given pressure. When we get to applications of thermodynamics we will then be concerned with the various forms of work like those shown in the table above.

This can be manipulated as Z x2 Z x2 Z V2 F w=− F dx = − Adx = − Pex dV (15.12)
112
.The force exerted on a gas by a piston is equal to the external pressure times the area of the piston: F = Pex A ⇒ Pex = F/A.11) A |{z} x1 x1 |{z} V1 dV
Pex
If Pex is independent of V then Z Z V2 Pex dV = −Pex w=−
V1
V2
V1
dV = −Pex 4V
(15. Rx Recall from physics that work is the (path) integral over force: w = − x12 F dx.

Maximum Work and Reversible changes
Now that we have learned about PV work we will consider the situation where the system does the maximum amount of work possible.1)
113
113
.16.
In the ﬁgure wA = −
Z
V2
V1
Patm dV = −Patm (V2 − V1 )
(16. Maximal Work: Reversible versus Irreversible changes
The value of w depends on Pex during the entire expansion.1.
16.

4)
Hence it is clear that |wB | > |wA | . That is.and wB = w1 + w2 . So. Namely Pgas = Pex . where w1 = − and Z
Vi
(16.3)
w2 = −
Vi
Patm dV = −Patm (V2 − Vi )
(16. Thus wrev is the maximum possible work that can be done in an expansion. there is always an intermediate equilibrium throughout the expansion. wrev = wmax .2)
V1
Patm+2W dV = −Patm+2W (Vi − V1 ) Z
V2
(16.
114
.5)
V1
This is the limiting case of path B in the previous ﬁgure. wrev = − Z
V2
Pgas dV
(16. Now consider case in the ﬁgure below
The expansion is reversible.

¡ dq ¢ ¡ dq ¢ e. However.b.2. dq amount of heat energy is transferred.8)
(16. heat capacity is a function of T .7) That is.16. CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property.. divide by mass to get speciﬁc heat 1 cV = m We will discuss heat capacity more later. To make an intensive property 1. it is not a constant. The heat capacity also depends on the conditions during the temperature change. divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2. µ dq dT ¶ (16. heat is related to temperature through the heat capacity dq dT n.6)
(16. Heat Capacity
Temperature and heat are diﬀerent.9)
V
115
. C(T ) = From this equation dq = C(t)dT. (16. when the temperature of a substance having a heat capacity C(t) is changed by dT. Temperature is not the amount of heat.. Temperature is an intensive property and heat is an extensive property.g.

The state of a pure. P independent then heat capacity is a function of T and P . (16.315 J K−1 mol−1 ) and n is the number of moles. The ideal gas equation of state can be expressed in terms of intensive variables only P Vm = RT . so we will focus our development of thermodynamics on simple systems. n m V
The equation of state can also be expressed in terms of density ρ = mass m/n) MP mP = . ρ= nRT RT
(and molar (16. homogeneous material (in the absence of external ﬁelds) is given by the values of any two intensive properties. (16. but behave in the same way as the more simple pure system.10)
where R is the gas constant (8.3. 16. P ).1.. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT .g. C(T.3. e. (More complicated systems require more than two independent variables. Equations of State
The macroscopic properties of matter are related to one another via a phenomenological equation of state.16. T .11) where Vm =
V .12)
116
.) The functional dependence of any property on the two independent variables is an equation of state.

16. V − nb V (16.13)
The parameter a attempts to account for the attractive forces among the particles The parameter b attempts to account for the repulsive forces among the particles b originates from hard sphere collisions (see ﬁgure):
117
.2.3. Example 2: The van der Waals Equation of State A more realistic equation of state was presented by van der Waals: P = nRT n2 a − 2.

Vm − b Vm (16. Some other equations of state are • Berthelot • Dieterici n2 a a nRT RT − − = 2 2 V − nb T V Vm − b T Vm
an a
P =
(16.In term of intensive variables P = a RT − 2.14)
16.3.15)
RT e− RT Vm nRT e− RT V = P = V − nb Vm − b nRT n2 a a RT −√ −√ = V − nb Vm − b T V (V − nb) T Vm (Vm − b)
(16. Other Equations of State The van der Waals equation of state is not the only one that has been proposed.16)
• Redlich-Kwang P = (16.3.17)
118
.

The temperature at which (for ﬁxed V and n) the pressure is zero is deﬁned as T =0K • T (Kelvin) = T (Celsius) + 273. Temperature scales • Celsius: A relative scale based on water (T = 0◦ C for melting ice and T = 100◦ C for boiling water) • Kelvin: An absolute temperature scale based on the ideal gas law. The Zeroth and First Laws of Thermodynamics
Over the course of the next two lectures we will discuss the four core laws of thermodyanmics.
17. Temperature and the Zeroth Law of Thermodynamics
Temperature tells us the direction of thermal energy (heat) ﬂow. Next time we will cover the second and third laws which both deal with entropy. which deal with temperature and total energy respectively.1. • Heat ﬂows from high T to Low T. Today we will cover the zeroth and ﬁrst laws.17.15 119
119
.

15 K and P = 1 atm. (Vm (SATP) = 24. Thermal equilibrium: If two systems are in contact along a diathermic wall and no heat ﬂows across the wall. (17. then the systems are in thermal equilibrium.
120
.1)
The zeroth law implies that if an arbitrary system.789 L/mol)
Diathermic wall: A wall that allows heat to ﬂow through it. (Vm (STP) = 22.15 K and P = 1 bar. C.414 L/mol) • standard ambient temperature and pressure (SATP): T = 298. The zeroth law of thermodynamics • Mathematical statement: If TA = TB and TB = TC . then TA = TC This the mathematical statement of transitivity • Verbal statement: If system A is in thermal equilibrium with system B and system B is in thermal equilibrium system C then system A is also in thermal equilibrium with system C.Standard conditions • standard temperature and pressure (STP): T = 273. Adiabatic wall: A wall the does not allow heat to ﬂow through it. is chosen as a thermometer then it will read the same temperature when it is in thermal contact along a diathermic wall with system A as when it is in thermal contact along a diathermic wall with system B.

one is concerned with the work done on the system (w) and the heat supplied to the system (q).2.. P )).g.2. The ﬁrst law of thermodynamics: • Mathematical statement: or in diﬀerential form dU = dq + dw (17. V (T. The value of the state function depends only on that given state and on no other possible state of the system.3)
4U = q + w
(17. 17.2)
• Verbal statement: The change in internal energy of a system is equal to the amount of work done on the system plus the amount of heat provided to the system. The First Law of Thermodynamics
Deﬁnitions: • State: the state of a system is deﬁned by specifying a minimum number in intensive variables • State Function: A function of the chosen independent variables that describes a property of the state (e.4)
121
.17. The energy of a system is called the internal energy (U) of the system.1. The internal energy state function For characterizing the change in energy of a system.
So for a system where all the work is P V work the ﬁrst law becomes Z V2 4U = q − Pex dV
V1
(17.

V ). the most convenient at this time are V and T.in diﬀerential form this is dU = dq − Pex dV (17.5)
Although U can be expressed as a function of any two state variables. U → U(T. ∂T The other slope. V ) is µ ¶ ¶ µ ∂U ∂U dU = dT + dV ∂T V ∂V T Consider adding heat at a constant volume then ¶ ¶ µ µ ∂U ∂U dT + dV = dq − Pex dV.7)
µ
(17.
A useful relation (derivation to come) is ¶ ¶ µ µ ∂U ∂P =T −P ∂V T ∂T V Example: A van der Waals gas n2 a nRT − 2 ⇒ P = V − nb V µ ∂P ∂T ¶ = nR V − nb
(17. The total diﬀerential of U (T.9)
(17.10)
V
122
. ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity.8)
.6)
(17. is called the internal pressure (it has no standard symbol). ¡ ∂U ¢
∂V T
(17. dU = ∂T V ∂V T So.

123
.11)
The equation of state for U : Express U in terms of T.so the useful relation becomes ¶ µ nRT nRT n2 a nR ∂U −P = − + 2 = T ∂V T V − nb V − nb V − nb V 2 na = + 2 V
(17. and P.12)
(17.13)
is the equation of state for U. A useful approximation is 4U = CV 4T which is valid for i) heat capacity nearly constant over 4T and with no phase transitions. ii) ideal gas or at constant volume. V. Hence ∂T ∂T ¶ ∙ µ ¸ ∂P − P dV dU = CV dT + T ∂T V
(17. Start with the total diﬀerential of U ¶ ¶ µ µ ∂U ∂U dT + dV dU = ∂T V ∂V T ¡ ∂U ¢ ¡ ¢ ¡ ¢ but ∂U V = CV and ∂V T = T ∂P V − P (useful relation).

Hence.3)
124
. A. is a measure of the disorder of the system and is expressed via Boltzmann’s equation S = k ln W (where W is the micocanonical partition function) We expressed Boltzmann’s law in terms of the more convenient canonical partition function as ¯ E S = + k ln Q.1.1) T ¯ Now. The Second and Third Laws of Thermodynamics
18.18. S. (18. Entropy and the Second Law of Thermodynamics
We learned from statistical mechanics that entropy. U A 1 − = (U − A).2)
1 (dU − dA) T 124
(18. and T are state functions. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q. the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E. S= So we may write dS = (18. T T T Since U. S is also a state function .

We learned previously that the maximum amount of work one can extract from the system is the work done during a reversible process.for an isothermal process.4)
Note: An alternative approach to thermodynamics which makes no reference to molecules or statistical mechanics is to simply begin by deﬁning entropy as dS ≡
dqrev T
The principle of Clausius • “The entropy of an isolated system will always increase in a spontaneous process” • Mathematical statement: (dS)U.V ≥ 0 For a general process: dU = dq − Pex dV For a reversible process Pex = P and dq = T dS so dU = T dS − P dV
125
. Recall the deﬁnition of Helmholtz free energy–the energy of the system available to do work. Hence dA = dwrev . For now let us limit the discussion to reversible processes. Then dS = 1 1 (dU − dwrev ) = (dqrev + dw rev − dw rev ) / / T T dqrev . (Reversible process) = T (18.

Thus for any spontaneous process T dS ≥ dq.
For some dU. (see ﬁgure) T dS is heat and −P dV is work only for reversible processes. but in general.Since U. This is a mathematical statement of the second law of thermodynamics (18. and V are state functions. • Case iii) P = Pex then (spontaneous) dV is zero so (P − Pex )dV is zero. • Case ii) P > Pex then (spontaneous) dV is positive so (P −Pex )dV is positive. dU = T dS − P dV holds for any process.5)
126
. T dS is not heat and −P dV is not work. dq − Pex dV = T dS − P dV ⇒ T dS = dq − Pex dV + P dV T dS = dq + (P − Pex ) dV • Case i) Pex > P then (spontaneous) dV is negative so (P −Pex )dV is positive. S. P. T.

So CV dT =⇒ 4S = dS = T Z
T2
(18.2. the second law has a number of equivalent statements 1.6)
From our earlier discussion of heat capacity dq = CV dT (CV since constant volume). dU = CV dT but also dU = T dS. The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius)
18. Spontaneous processes are irreversible in character. The entropy of the universe is increasing 5. The Third Law of Thermodynamics
Consider the ﬁrst law for a reversible change at constant volume.1. 2. dU = dq + dw = dq − Pex dV (18.8)
127
. A useful perpetual motion machine does not exist.18. 4. Work must be done to transfer heat from a cold to a hot reservoir. So.1. Statements of the Second Law Unlike the ﬁrst law. T
(18. 6.7)
T1
CV dT. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work. 3.

A very similar derivation can be done for a reversible change at constant pressure (we can not do it quite yet) to yield Z T2 CP dT (18.9) 4S = T T1 18. Consider the heat capacity near T → 0.
128
.11)
Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0
(18. Ar. a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e. For S0 to have signiﬁcance
CP T
must be ﬁnite (not inﬁnite) as T → 0.g. Thus CP → 0.1. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy. However.10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z
T2
0
CP dT T
(18.). Alternative statement of the third law: Absolute zero is unattainable.2. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18.g. O2 etc. S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e.12)
From a macroscopic point of view S0 is arbitrary... CO).

∗ ∗ CP m . That is at low temperatures heat capacity goes as the cube of the temperature. a = CP m /T ∗3 . an inﬁnitesimal amount of heat causes an inﬁnite change in temperature.
In other words. So.
18.
In view of what we have learned about ﬂuctuations.2.
129
. (Debye) Postulate: CP m = aT 3 . Debye’s Law Heat capacity data only goes down so far. the ever present random ﬂuctuations in energy provide the inﬁnitesimal amount of heat and so you can never reach absolute zero corresponding to an average energy of zero.2. So one needs a theoretical extrapolation down to T = 0. T ∗ are the lowest temperature data points.But CP =
dq dT
→ 0 implies
dT dq
→ ∞.

3. the behavior of the macrosystem deﬁnitely changes if you replace t with −t.13)
0
Entropy and the second law give a direction to time. Thus the simple fact that you have an enormous number of particles induces a perceived asymmetry in time. Times Arrow
∗ CP C =aT 3 CP m dT P m = T T ∗3 0 ¯T ∗ ∗ ∗ CP m T 3 ¯ ¯ = CP m . We know which picture was taken ﬁrst. Both Newton’s laws and Quantum dynamics (next semester) are the same if you replace t with −t.The molar entropy is Sm (T ) = =
∗
Z
18.
130
. The interesting thing is that each molecule in a macroscopic system obeys time invariant dynamics. For example. if we see a picture of your PChem book in mint condition and we see a picture of your PChem book all battered and beaten. Yet. T ∗3 3 ¯ 3 0
T∗
Z
T∗
T 2 dT
(18.

The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.
Equations
• The Boltzmann equation is • The Boltzmann distribution : g e−β i P i −β j gj e X
j
j
S = k ln W.
(18.Key Equations for Exam 3
Listed here are some of the key equations for Exam 3.14)
(18. This section should not substitute for your studying of the rest of this material.16)
131
131
.15)
• The canonical partition function is Q=
gj e−βEj
(18. The equations are collected here simply for handy reference for you while working the problem sets.

• The Rotational Partition Function (linear molecules) is T qrot ≈ . σθr
2
(18.V ¡ ∂Q ¢ 1 1 = βQ ∂V n.21)
• The ensemble average of any property is given by 1 X ¯ Oi gi e−β i .20)
h where θr ≡ 8π2 Ik (I is the moment of inertia) and σ is the so-called symmetry number in which σ = 1 for unsymmetrical molecules and σ = 2 for symmetrical molecules
• The Vibrational Partition Function is qvib = 1 . 2 sinh 1 β~ω 2 (18.β
132
.18) Λ where h Λ≡ √ (18.β = β
³
=−
+ k ln Q ¡ ∂ ln Q ¢
∂V
³
∂ ln Q ∂β
´
n.17) N! • The Translational Partition Function V qtrans = 3 (18.• The relation between the partition function and the molecular partition function is qN Q = mol .22)
• The relations between the canonical partition function and the thermodynamics variables are Internal energy Entropy Helmholtz Free Energy A = −kT³ln Q ´
1 U = −Q ∂Q ∂β
S
Pressure
P
n. (18.V ´ ∂ ln Q = −kβ ∂β n.19) 2πmkT is the thermal de Broglie wavelength.V
n. O= Q i
(18.

27)
(18.26)
(18.24)
4U = q + w.23)
(18. Also.25)
(18.29)
• Debye’s law for entropy at very low temperatures Sm (T ∗ ) =
∗ CP m . dq = C(t)dT.
133
.
(18. • The second law • The third law T dS ≥ dq.• P V work is • Heat capacity: • General forms of the ﬁrst law:
dw = −P dV. dU = T dS − P dV.28)
0
CP dT + S0 T
(18.30)
∗ where CP m is the molar heat capacity at the lowest temperature for which there is data. S(T2 ) = Z
T2
(18. in diﬀerential form this is dU = dq − Pex dV. 3
(18.

Part IV Basics of Thermodynamics
134
134
.

here too is energy the key property with which to work. K. So far we have encountered two state functions which characterize the energy of a macroscopic system–the internal energy and.
19.
135
135
. The Other Important State Functions of Thermodynamics
As was the case in quantum mechanics. and kinetics–topics we will encounter throughout the year. electrochemistry. (which you are familiar with from general chemistry) serves are a common point which connects thermodynamics. brieﬂy the Helmholtz free energy.19. the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year.1. The equilibrium constant for a thermodynamic process. Consequently. Auxillary Functions and Maxwell Relations
We have stated that thermodynamics as we are studying it deals with states in equilibrium or transitions between equilibrium states.

V ) Unfortunately S can not be directly measured and most often P is a more convenient variable than V Because of this fact.
136
. (T and V ) and (T and P ) The table below lists these state functions State function Internal Energy Enthalpy Helmholtz free energy Gibbs free energy Symbol Natural variables U H A G S S T T and V and P and V and P Deﬁnition H ≡ U + PV A ≡ U − TS G ≡ H − TS Units energy energy energy energy
We consider each of these functions in turn
19. This is U = U(S.From the ﬁrst law as stated as dU = T dS − P dV (19. Enthalpy
We want a state function whose natural variables are S and P Let us try the deﬁnition H ≡ U + P V. The other pairs of natural variables being (S and P ).2. it is handy to deﬁne state functions which have diﬀerent pairs of natural variables.1)
we say that the natural (most convenient) variables for the equation of state for U are S and V . so that no mater what situation arises we have convenient equations of state to work with.

So a change in enthalpy is the change in internal energy adjusted for the P V work done. 19. The system does work during the expansion.2)
/ / dH = T dS − P dV + P dV + V dP
= T dS + V dP. in doing so it must lose energy. Since the process is adiabatic no heat energy can ﬂow in to compensate for the work done and the gas cools. Helmholtz Free Energy
Now we want a state function whose natural variables are T and V
137
.3. The total internal energy decreases.Now formally dH = dU + d(P V ) = dU + P dV + V dP.3)
Enthalpy is the total energy of the system minus the pressure volume energy. consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. but dU = T dS − P dV. Hence Enthalpy does indeed have the desired natural variables.1. If the process occurs at constant pressure then the enthalpy change is the heat given oﬀ or taken in.2. As Freshmen we learn this as 4H = qp . The enthalpy of the system on the other hand does not change–it is the internal energy adjusted by an amount of energy equal to the P V work done by the system. For example. so (19.
19. Heuristic deﬁnition:
(19.

1.5)
Hence Helmholtz free energy does indeed have the desired natural variables. so (19.7) (19.Let us try the deﬁnition A ≡ U − T S.4)
/ / dA = T dS − P dV − T dS − SdT
= −P dV − SdT.3.4. Hence Gibbs free energy does indeed have the desired natural variables. Formally dA = dU − d(T S) = dU − T dS − SdT. so dG = T dS + V dP − T dS − SdT / / = V dP − SdT. Now formally dG = dH + d(T S) = dH − T dS − SdT.
19. but dU = T dS − P dV. 19. (19. but from above dH = T dS + V dP.6)
138
.
(19. Heuristic deﬁnition: As we have said before Helmholtz free energy is the energy of the system which is available to do work–It is the internal energy minus that energy which is “used up” by the random thermal motion of the molecules. Gibbs Free Energy
Finally we want a state function whose natural variables are T and P Let us try the deﬁnition G ≡ H − T S.

The Relationship Between CP and CV To ﬁnd how CP and CV are related we begin with dH = T dS + V dP at constant pressure and reversible conditions dH = T dS dH = dq but dq = CP dT (19. ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (19.10) (19.13)
P
139
. (19.5.
19.19.11) CP = ∂T P So.1.12) ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V .9) (19.4.5.8)
The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H . Heat Capacity of Gases
19. Heuristic deﬁnition: Gibbs free energy is the energy of the system which is available to do non P V work–It is the internal minus both that energy which is “used up” by the random thermal motion of the molecules and used up in doing the P V work. Use an identity of partial derivatives ∂T ∂T µ µ ∂U ∂T ¶ =
P
µ
∂U ∂T
¶
+
V
µ
∂U ∂V
¶ µ
T
∂V ∂T
¶
(19.1.

The Maxwell Relations
Summary of thermodynamic relations we’ve seen so far Deﬁnitions and relations: • H = U + PV
140
. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ
P
¶
(19.15)
∂P ∂T
¶
(19. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .18)
19.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (19.16)
V
Example: Ideal gases 1.17) ∂T P ∂T V nRT nR nR = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R (19. Ideal gas (equation of state: P V = nRT ): This equation is easily made explicit in either P or V so we don’t need any of the above replacements ¶ µ ¶ µ ∂P ∂V CP = CV + T (19.6.

• A = U − TS • G = H − TS • CV = ¡ ∂U ¢
∂T V
.
CP =
¡ ∂H ¢
∂T
P
basic equations dU = T dS − P dV dH = T dS + V dP dA = −P dV − SdT dG = V dP − SdT
Maxwell relations ¡ ∂T ¢ ¡ ¢ = − ∂P V ∂V S ¡ ∂T ¢ ¡ ∂S ¢ = ∂V P ∂P S ∂S ¡ ∂S ¢ ¡ ¢ = + ∂P V ∂V T ¡ ∂S ¢ ¡ ∂T ¢ = − ∂V P ∂P T ∂T
working equations £ ¡ ¢ ¤ dU = CV dT + T ∂P V − P dV ∂T £ ¡ ¢ ¤ dH = CP dT − T ∂V P − V dP ∂T ¡ ¢ dS = CV dT + ∂P V dV T ¡ ∂T ¢ dS = CP dT − ∂V P dP T ∂T
We will get plenty of practice with derivations based on these equations and on the properties of partial derivatives. (See handout and Homework)
141
.

2)
.1. The tendency to minimize energy 2.V = 0. Hence at equilibrium (dA)T. (dA)T. For chemistry it is most often more convenient to use Gibbs free energy The total diﬀerential of G is dG = dH − T dS − SdT = dq − Pex dV + P dV + V dP − T dS − SdT 142
142
(20. The tendency to maximize entropy
Let us begin with Helmholtz free energy The total diﬀerential of A is (A = U − T S) dA = dU − T dS − SdT = dq − Pex dV − T dS − SdT For constant T and V.V ≤ 0 for a spontaneous process.V = dq − T dS From the second law.20. Chemical Potential
20. T dS ≥ dq for a spontaneous process. (dA)T. Spontaneity of processes
Two factors drive spontaneous processes 1.1)
(20.

6) (20. Note free energy provides no information about how fast a process proceeds to equilibrium. Plugging these into the total diﬀerentials of free energy gives dA = −SdT − P dV and dG = −SdT + V dP (20. (20.P = 0. Returning to the total diﬀerentials of free energy. (dG)T.P ≤ 0 for a spontaneous process. dA = dU − T dS − SdT and dG = dH − T dS − SdT. So free energy provides a measure of the thermodynamic driving force towards equilibrium. T dS ≥ dq for a spontaneous process.For constant T and P = Pex .4) Expressing dU and dH generally as dU = T dS − P dV and dH = T dS + V dP (remember that in general T dS cannot be identiﬁed with dq and P dV cannot be identiﬁed with −w).5) (20. (dG)T.3)
143
. Hence at equilibrium (dG)T. The free energy functions are the workhorses of applied thermodynamics so we want to get a feel for them.P = dq − T dS Again from the second law.

For a reversible process dq = T dS and work is maximal. As we have stated in words a number of times before. Hence (dA)T = dwmax =⇒ (4A)T = wmax . The total diﬀerential of G is also dG = dq + dw + P dV + V dP − T dS − SdT. The total diﬀerential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT.
20.8)
(20. Chemical potential
What if the amount of substance can change?
144
.P = wmax
(20. as stated earlier.These expressions are quite general. For reversible processes q = T dS and this becomes
0 0 (dG)T. For constant T and P = Pex .9)
(20.2.7)
(20. but i) only P V work and ii) closed systems.10)
So. The total diﬀerential of A is also dA = dq + dw − T dS − SdT. (dG)T.P = dq + w0 − T dS.P = dwmax =⇒ (4G)T. the Gibbs free energy is the energy of the system available to do non-P V work. In general dw = dw0 − Pex dV where dw0 is the non-P V work.

13)
= −SdT − P dV + P dV + V dP + μdn / / / / = −SdT + V dP + μdn. n) = dT + dV + dn (20. V.T
145
.n ∂n V.14)
P.Extensive properties depend on the amount of “stuﬀ” For example A(T. V ) now becomes A(T.n
P.T
.n ∂V T. V.n
T. but from dG = µ ∂G ∂T ¶ dT + µ ∂G ∂P ¶ dP + µ ∂G ∂n ¶ dn (20.T
. • It deﬁnes the chemical potential μ ≡ So we can also write dA = −SdT − P dV + μdn What about the relation of the chemical potential to Gibbs’ free energy? G = H − T S = U − T S + P V = A + P V so.
• This is a measure of the change in Helmholtz free energy of a system (at constant T and V ) with the change in the amount of material. this is a measure of the potential to change the amount of material.T Let’s focus on the slope ¡ ∂A ¢
∂n V. • Physically.11) ∂T V. | {z }
=A
¡ ∂A ¢
∂n V. n) and the total diﬀerential becomes µ ¶ ¶ µ µ ¶ ∂A ∂A ∂A dA(T.12)
dG = dA + P dV + V dP
(20.
(20.

3.g. concentration etc.). μ is also a measure of the change in Gibbs free energy of a system (at constant T and P ) with the change in the amount of material and it still has the same physical meaning. (Gm = μ)
20. The mathematical deﬁnition of activity ai of some species i is implicitly stated as
ζ→ζ
lim ª
ai =1 g(ζ)
(20. The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical potential.we see that μ=
µ
∂G ∂n
¶
. To account for this one must introduce the concept of activity and the activity coeﬃcient. and ζ ª is the value of ζ at the reference state. a solute is dissolved in a solvent.
146
. Activity is hard to deﬁne in words and indeed it has an awkward mathematical deﬁnition as we will soon see. mole fraction. pressure. The activity coeﬃcient has a more convenient deﬁnition which is that it is the measure of how a particular real system deviates from some reference system which is usually taken to be ideal.. Activity and the Activity coeﬃcient
When.
(20.T
So.16)
where g(ζ) is any reference function (e. for example. there exist complicated interactions which cause deviations from ideal behavior.15)
P.

but it is often the case that the reference state is chosen to be some ideal state. γi ≡ which we can rearrange as ai = γ i g(ζ). Note: the activity of gases as referenced to pressure has the special name fugacity (fugacity is a special case of activity). (20. if we are talking about a gas we will mostly likely choose the ideal gas law in terms of pressure (P = nRT /V ) as our reference function and the reference state being when P = 0 since we know all gases behave ideally in the limit of zero pressure. Reference States Thermodynamics is founded on the concept of energy which we know to have an arbitrary scale. Because of this it is always necessary to specify a reference state to which our real state can be compared.1. For example. we can deﬁne are zero of energy any where we want.This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit. ai g(ζ) (20.3.18) The deﬁnition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) 20. That is.17)
147
. Let us consider the activity of a real gas for the above reference function and reference state. The choice of this state is completely up to us.

2.20)
Rather than referencing to the standard state one can also reference to any convenient “ideal” state. μi − μª = RT ln ai . The deviation of the chemical potential at the state of interest versus at the reference state is determined by the activity at the current state (the activity at the reference state is unity by deﬁnition).19)
Thus the activity of our real gas is given by the activity coeﬃcient times the pressure of an ideal gas under the same conditions. Activity and the Chemical Potential One cannot measure absolute chemical potentials. i (20. i i i i i i (20. Based on the condition that γ → 1 as we approach the reference state (P = 0 in this case) we see that the activity (or fugacity) of a real gas becomes equal to pressure for low pressures
20.21) i and for the ideal state μid = μª + RT ln aid ⇒ μª = μid − RT ln aid . so γ= a ⇒ a = γP.22)
148
.3. This ideal state is in turn referenced to the standard state. only relative potentials can be measured. P (20. For the state of interest μi = μª + RT ln ai (20.Our reference function is very simple: g(ζ) = ζ = P . By convention we chose a standard state and measure relative to that state.

so μid − μª = RT ln μid = μª + RT ln P. μid → μª ).29)
149
.24)
Now we integrate from the reference state to the current state of interest Z Z RT id dP. Lets say our gas is not ideal.Thus.26)
(20.28) (20. then at a given pressure μ = μª + RT ln a. μi = μid − RT ln aid + RT ln ai i i (20. (20. (20. (20. Thus μ = μª + RT ln f.23)
μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai
Example: Real and ideal gases at constant temperature.25) dμ = μª Pª P This gives P .27)
For gases activity is usually called fugacity and given the symbol f . (Note that as P → 1. Starting from the begining dμ
id
dμid = Vm dP RT dP. so a = f for real gasses. but any pressure. dμid = P
z}|{ = dGm = −Sm dT + Vm dP
=0
(20. Pª The usual standard state is the ideal gas at P ª = 1.

We have an ideal gas so.e. We add this energy per mole term to the chemical potential (which is free energy per mole) thus at equilibrium μid (0) = μid (h) + Mgh Referencing to the reference state we get
ª ª μ/ = μ/ + RT ln Ph + Mgh
(20. i.30)
and at elevation h
z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph
=0
(20. P Example: The barometric equation for an ideal gas. P ª = 1 atm. μid = μª + RT ln P where we will take the reference state to be at sea level. So at sea level
id ª
(20.
150
.Lets say that instead of referencing to the ideal gas at P = 1.33)
(20.34)
RT ln Ph = −Mgh Ph = e
−M gh RT
The last line is the barometric equation and it shows that pressure is exponentially decreasing function of altitude. This is easily done by using μª = μid − RT ln P in the above equation for μ. we want to reference to the ideal gas at the current pressure P.31) (20.32)
The gas ﬁelds the gravitational force which gives it a potential energy per mole of Mgh at height h. μ = μid − RT ln P + RT ln f f μ = μid + RT ln .

Ka . Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now. if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition. aA (21. for this process.21. The quantity aB deﬁnes the equilibrium constant.1)
151
151
. μA = μª + RT ln aA A and μB = μª + RT ln aB B So the equilibrium condition becomes μª + RT ln aA = μª + RT ln aB A B −4μª = μª − μª = RT ln aB − RT ln aA A B aB −4μª = RT ln aA Since chemical potential is free energy per mole.2) (21. Equilibrium
First let us consider the equilibrium A B.3) (21.

8) A B C D Rearranging gives z }| { ac ad aμª + bμª − cμª − dμª = RT ln C D A B C D aa ab A B
≡−4rx n Gª
(21. aA
Again multiplying by n gives 4G = 4Gª + nRT ln aB .Say the system A → B is not in equilibrium then we can not write μA = μB but we can write
4μ
Proceeding as above we get
z }| { μA + μB − μA = μB
(21. aA
If the 4G < 0 then the transition A → B proceeds spontaneously as written. In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (21.9)
152
.7)
(21.4)
μª + RT ln aA + 4μ = μª + RT ln aB A B
(21. The equilibrium condition is aμA + bμB = cμC + dμD .5)
4μ = μª − μª + RT ln aB − +RT ln aA B A aB 4μ = 4μª + RT ln . Consider a more complicated equilibrium aA + bB cC + dD.6)
(21.

(21. 21.0. The Partition Coeﬃcient Up to now we have only considered miscible solutions.
153
.
21. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture.10)
Note: n is absent in the above since the molar values are implied by the stoichiometry.12)
If the reactants are solutes then as the solution is diluted all the activity coeﬃcients 0 go to unity and KC → Ka . ¶
(21.0.11)
which is related to Ka by Ka =
0 KC
.4.the equilibrium constant is ac ad Ka = C D =⇒ 4Gª = −RT ln Ka aa ab A B (21.3. Equilibrium constants in terms of KC Equilibrium constant in terms of a condensed phase concentration:
0 KC =
[C]c [D]d [A]a [B]b µ γc γd C D γa γb A B
.

14) (21.16)
Knowledge of the partition function is important on the delivery of drugs because. the drugs must transfer between an aqueous phase and a oil phase. The equilibrium constant for this process has a special α α→β β β/α name.13)
where. to enter the body. P β/α ≡ Kpart . for species A in the α—β mixture. α→β (21. 4Gª ≡ Gª −Gª . [A]α
(21. We can solve for the partition coeﬃcient to yield P For low concentrations P β/α '
β/α
4G α→β aβ = A = e− nRT . it is called the partition coeﬃcient.
154
. α aA ª
(21.15)
[A]β .The equilibrium equation is Aα Aβ The equilibrium expression for this process is 4Gα→β = 0 = 4Gª − nRT ln Ka .

17)
Partition coeﬃcient
o/w
Delivery mechanism
low Ppart (likes water) injection o/w medium Ppart oral o/w high Ppart (likes oil) skin patch/ointment
Factors other than the partition coeﬃcient inﬂuence the drug delivery choice.For most drugs 0 < Ppart < 4
o/w
(21. can the drug handle the acidic environment of the stomach?
155
. For example.

4rxn H > 0 for Endothermic reactions.22.A − bSm. For any extensive property • 4rxn (Property) = property of products − property of reactants • Example — Reaction: aA+bB= cC+dD — 4rxn S = cSm.1.D − aSm. After chemical reactions take place the system is in a ﬁnal “product” thermodynamic state that is in general diﬀerent from the initial “reactant” state.C + dSm. 156
156
(22. Chemical Reactions
Up to now we have only been considering systems in the absence of chemical reactions. Heats of Reactions
Exothermic reaction: heat is given oﬀ to the surroundings Endothermic reaction: heat is given taken in from the surroundings At constant pressure (Pex = P q = 4rxn U − w = 4rxn U − P 4rxn V = 4rxn H 4rxn H < 0 for Exothermic reactions.B
22.1)
.

83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent.63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410.830 kJ 2 H2 O(liq)→H2 O(gas)
4rxn H ª = −241. O2 .2)
157
.818 kJ 2 H2 + 1 O2 = H2 O(liq) 4f H ª = −285.830) = 44.1.49 kJ
The heat of formation 4f H ª is the 4rxn H at STP in forming a compound from its constituent atoms in their natural states. This direct reaction is not easy but it can be done in steps C2 H2 + 5 O2 → 2CO2 +H2 O(liq) 4rxn H ª = −1299. C(graphite) are examples of atoms in their natural state.97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285.22. Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) +
T1
(22. where ν i is the stoichiometric factor of the ith com-
Example: H2 O(liq)→H2 O(gas) at SATP H2 + 1 O2 = H2 O(gas) 4f H ª = −241.2. P
i
ν i 4f H(i).1. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 .818 − (−285. H2 .1.012 kJ
22.

6)
4rxn G = 4rxn Gª + RT ln Q. 4rxn G = i
i i 4rx n Gª
X
i
ν i μi . As we saw before μi can be deﬁned in terms of activity μi = μª + RT ln ai . Reversible reactions
Recall the requirement for a spontaneous change: 4G < 0 for constant T and P. where Q ≡
i
aν i is the activity quotient. For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (22. 4rxn G = 0 and Q = Ka (Thermodynamic equilibrium constant). i So.
158
.i for pure substance i).4)
(22.
(22. 4rxn G = G(products) − G(reactants) = (remember μi = Gm.3)
(22.22. z }| { X X ν i μª + RT ν i ln ai . Ka depends on T but is independent of P.5)
Using the property of logarithms: a ln x + b ln y = ln(xa y b ) the above expression becomes 4rxn G = 4rxn Gª + RT ln Q Y
i
aν i i
(22. i
At equilibrium.7)
• Note that the activity of any pure solid or liquid is for all practical purposes equal to 1.2.

Temperature Dependence of Ka
Starting with G =´H − T S or G/T = H/T − S.11)
(22. ai = useful relation KP =
Pi Pª
=
Xi P Pª
(P ª = 1 bar) This leads to the sometimes
or more generally KP = Ka (P ª )
c d ¡ ¢c+d−a−b PC PD (P ª aC )c (P ª aD )d = = Ka P ª .14)
T1
For a reasonably small range T2 − T1 this is well approximated by µ ¶ ª 4rxn Hm 1 1 − ln Ka (T2 ) = ln Ka (T1 ) − R T2 T1
(22. ∂(1/T P Applying this to 4rxn H ª 4rxn Gª = − 4rxn S T T gives ¶ µ ∂(4rxn Gª /T ) = 4rxn H ª ∂(1/T ) P ª Using 4rxn G = −RT ln Ka .
So at equilibrium.10)
(22.12)
=
dT d d(1/T ) dT
d = −T 2 dT )
4rxn H ª d ln Ka = dT RT 2 Integration gives 1 ln Ka (T2 ) = ln Ka (T1 ) + R Z
T2 ª 4rxn Hm T2
(22. we get ¶ µ 4rxn H ª ∂ ln Ka ind.15)
159
.13)
(22.3.• For ideal gases. ³ From this ∂(G/T)) = H.8)
νi
. d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using
d d(1/T )
(22. (22. 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka . a b PA PB (P ª aA )a (P ª aB )b
i
(22.9)
22.

RT
KC = KP (RT )−4υg
¡ RT ¢−4υg
V
relation to Ka – µ
Ka −4υ g Kγ P ª ¶
situation used when an exact answer is needed gas reactions
activity(products) activity(reactants) partial pressure(products) partial pressure(reactants) mole fraction(products) mole fraction(reactants) moles(products) moles(reactants) concentration(products) concentration(reactants)
µ
µ
Ka −4υ g Kγ P ª
Ka −4υ g Kγ P ª
Ka −4υ g Kγ P ª
¶
¶
P
V
−4υ g
when eq. • From Pj = Xj P . Kn = KP
• From concentration Cj = Equilibrium “constants” “constants” expression Ka KP KX Kn KC
nj V
=
Pj .22. Extent of Reaction
There are other equilibrium “constants” that are used in the literature. P is known when V is known and constant when concentration known
(RT )−4υg
¡ RT ¢−4υg
160
.4. KX = KP P −4υg
V • From nj = Pj RT (ideal gas approximation).

(23. Ionics
Many chemical processes involve electrolytes and or acids and bases.1)
where v+ (v− ) is the number of cations (anions) and z+ (z− ) is the charge on the cation (anion). The chemical potential for the salt may be written in terms of the chemical potential for each of the ions: μsalt = v+ μ+ + v− μ− To determine the activity we start with μj − μª j . Ionic Activities
Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq).3) (23. ln aj = RT and ln asalt = j = + or − (23. To understand these processes we must know something about how ions behave in solution. RT
(23.23.
23.4)
161
161
.1.2)
μsalt − μª salt .

ln asalt = v+ ln a+ + v− ln a− or. 23.9) The quantity a± is the mean ionic activity. (23. alternatively.10)
v
v
1/v
. (23.5)
So.11)
162
.7)
It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties.1.1. asalt = av+ av−
(23. Ionic activity coeﬃcients The activity coeﬃcients for ionic solutions can also be deﬁned via a+ = γ + m+ . a− = γ − m− .Substituting the expression for μsalt into this gives ln asalt v+ μ+ − v− μ− + v+ μª − v− μª + − = RT v+ μ+ − v+ μª v− μ− − v− μª + − + = RT RT | {z } | {z }
v+ ln a+ v− ln a−
(23.6)
(23.8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± . where m+ = v+ m and m− = v− m.
(23. The mean ionic activity coeﬃcient is
+ − γ ± = (γ + γ − )
(23. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt .

16)
163
.2. One can use the colligative properties to measure the ionic activity coeﬃcients. m0 0 where j = 1 − φ. γ + and γ − cannot be measured individually.13)
(23. It is convenient to redeﬁne the osmotic coeﬃcient as φ= −1000 g/kg ln a1 . Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 . Results from Debye—Hückel theory: point charge in a continuum The Debye—Hückel equation: √ −α |z+ z− | I √ . So. Similarly freezing point depression is redeﬁned as θ = vφKf m. vmM1 (23.12)
where the subscript 1 refers to the solvent.14)
23. Theory of Electrolytic Solutions
Ionic strength is deﬁned as I= 1X 2 z mi . (23.The quantities a+ . vφ corresponds to the empirical factor i discussed earlier. 2 i i
(23. a− . ln γ ± = 1 − Ba0 I
(23.15)
where z is the charge of the ion and m its concentration.

It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± . 2 A useful empirical approximation is to set Ba0 = 1 and to add an empirical correction to get the : √ µ 2 ¶ 2 v+ + v− −α |z+ z− | I √ ln γ ± = + 2βm . (23. Notice that the parameters α and B depend only on the solvent.19) This gives the dependence of ln γ ± for dilute solutions (m → 0).3.20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0. ρ• is the density of the pure solvent.1
23. I is given by the rate of change (in time) of charge. (23.17)
8πLe2 ρ• . ε is the dielectric constant for the pure solvent and L is Avogadro’s number.21)
164
. which is observed exP perimentally (recall I = 1 i zi2 mi ). (23.where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 . Q: I= dQ dt (23.18) 1000εkT a0 is the radius of closest approach. e is the charge on the electron. (23. One important approximation to this equation is to neglect the B term to get the Debye—Hukel limiting Law (DHLL): √ ln γ ± = −α |z+ z− | I. Ion Mobility
Current.

23)
Conductance is the inverse of the resistance (R−1 ).602177 × 10−19 C.3. Ion mobility
165
. ε: w = −εQ (23.22) Power is given by the product of the voltage and the current: p = −εI Resistance is given by the ratio of the voltage to current: R= ε I (23.1.(Electrical) work. Some relevant constants • charge of an electron e = 1. w. is required to move a change through a potential (or voltage). • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 23.

30)
The ions quickly reach terminal velocity. −. E = Also recall Newton’s law
dε . dt
(23.28)
Fi = mai = m
dvi = zi eE.The total current passing through an ionic solution is determined by the sum of the current carried by the cations and by the anions I = I+ + I− Now Ii = where i = +. i.25)
Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum)
(23. (23.27)
(23.
166
.26)
(23.. zi eE zi eE = f vi =⇒ vi = . Hence Fi = 0. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution). (23.e.24)
dQi dNi = |zi | e . dt dt
(23.29)
The moving ions experience a viscous drag f that is proportional to their velocities. the viscous drag equals the Coulomb force. For uniform ion velocity (vi ) the number of ions arriving at the electrode during any given time interval 4t is 4Ni = so Ii = |zi | e Recall Coulomb’s law Fi = zi eE.31) f The drag f has three basic origins. where E is the electric ﬁeld. dx
(23.

1.
167
. • oppositely charged ions “pull” at each other
3. Relaxation eﬀects • solvation shell must re-adjust as ion moves. Electrophoretic eﬀect. Stoke’s Law type force • “spherical” ion moving through a continuous medium • this contribution is independent of the other ions 2. a “dressed” ion.

34)
Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to produce ν + cations and ν − anions. (23. vi l . then each mole of salt gives: N+ = αν + Ln and N− = αν − Ln. The current then becomes Ii = |zi | e αν i Ln ui ε F=Le ε A = αν i n |zi | ui AF V l Vl (23. =1 z }| { / ν +/ |z+ | u+ A / Vεl / F / ν + |z+ | u+ u+ α n I+ = = = (23. where l is the separation of the l plates. V l (23.32) E For the case for parallel plate capacitors E = ε . ui which is the ion’s velocity per ﬁeld.36) I− / ν −/ |z− | u− A / Vεl α n / F / ν − |z− | u− u− Thus the ratio of the currents is determined by simply the ratio of the mobilities.A more fundamental quantity than ion velocity is the ion mobility.
168
. (23.35)
It is of interest to determine the ratio of the current carried by the cation versus the anion. vi ui = .33) ui = ε Here the current carried by ion i is Ii = |zi | e Ni ui ε A . So.

Thermodynamics of Solvation
An extremely important application of thermodynamics is to that of ion solvation. Primarily we will determine 4Gv→s ≡ Gion in solv. Solvation describes how a solute dissolves in a solvent. − Gion in vac . The way to investigate the ion—solvent interaction upon solvation from a thermodynamics point of view is to consider the change in the properties of the ion in a vacuum versus the ion in solution. Of course this is an approximation and numerous statistical mechanical models for solvents which incorporate a more realistic structure can be used. We will focus on ions in solution. 4Gv→s can be determined by calculating the reversible work done in transferring an ion into the bulk of the solvent.
169
169
. Since Gibbs free energy corresponds to non-P V work. As a basic treatment of solvation we shall consider the solvent as a non-structural continuum and the ion as a charged particle. but we will stick with this simple thermodynamic model.24.

The Born Model
The Born model is a simple solvation model in which the ions are taken to be charged spheres and the solvent is take to be a continuum with dielectric constant εs
170
.1.24.

4Gv→s for the Born model is obtained by considering the following contribution to the work of ion transfer from the vacuum state to the solvated state (see ﬁgure) • Begin with the state in which the charged sphere (the ion) is in a vacuum. done in discharging the sphere. done in charging the sphere which is now in the solvent. wch . wdis . • Determine the work.
171
. wtr = 0. • Determine the work. • Assume the uncharged sphere can pass from the (neutral) vacuum to the neutral solvent without doing any work. (This is an approximation).

4Gv→s = wdis + wtr + wch = wdis + wch (24.So.
172
.1)
Work done in discharging the sphere: The act of discharging a sphere involves bringing out to inﬁnity from the surface inﬁnitesimal amounts of charge. The work done is discharging is some what complicated since as one removes the charge the work done in removing more charge changes according to the amount of charge currently on the sphere.

2)
where z is the oxidation state of the ion.4)
The above expression is 4Gv→s /ion. wch = + (ze)2 8π 0 εs ri (24.5)
173
.3)
24.1.This is expressed mathematically as Z 0Z ∞ σ wdis = drdσ 2 ze ri 4π 0 r Z 0 σ dσ = ze 4π 0 ri (ze)2 . Free Energy of Solvation for the Born Model Combining the above two expression for work gives 4Gv→s = − (ze)2 (ze)2 + 8π 0 ri 8π 0 εs ri µ ¶ (ze)2 1 = −1 8π 0 ri εs N (ze)2 = 8π 0 ri µ ¶ 1 −1 εs (24. So. = − 8π 0 ri
(24. e is the charge of the electron.1. Work done in charging the sphere: The only diﬀerence in charging the sphere is that the sign of the work will be diﬀerent and that since we are charging in a solvent we must multiply the permittivity of free space by the dielectric constant of the solvent. For n moles of ions (nL = N) 4Gv→s (24. ri is the radius of the sphere (ion) and 0 is the permittivity of free space.

Ion Transfer Between Phases We can quickly generalize the Born model to describe ion transfer between phases in a solution of two immiscible phases Consider an immiscible solution of two phases α and β having dielectric constants εα and εβ .The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0.1. Enthalpy and Entropy of Solvation We may employ the standard thermodynamic relations which we have derived earlier to obtain the entropy and enthalpy for the Born model.
174
.2. Since Gibbs free energy is a state function we can write the change in free energy for transfer of an ion form the β phase to the α phase as z }| { 4Gβ→v + 4Gv→α µ µ ¶ ¶ N (ze)2 1 N (ze)2 1 = − −1 + −1 8π 0 ri εβ 8π 0 ri εα µ ¶ 1 N (ze)2 1 − = 8π 0 ri εα εβ
=−4Gv →β
4Gβ→α =
(24.
24.6)
The Partition Coeﬃcient We can now write the partition coeﬃcient for the Born model as
α/β Pi
=e
−4Gª β→α nRT
=e
− 8πr
L(ze)2 i 0 RT
1 − ε1 εα β
(24. Thus ions always exist more stably in solution than in a vacuum.1.7)
24.3.

the Born model does not make quantitatively correct predictions in many cases. We simply list here several phenomena that more sophisticated theories of solvation must consider
175
. Unfortunately however.11)
24. Corrections to the Born Model
The Born model is very valuable because of its simplicity–qualitative statements about solvation and ion transfer between phases can be made. (24.10) = 4Sv→s = − 8π 0 ri ∂T εs 8π 0 ri ε2 ∂T s Enthalpy is obtained via the relation: 4Hv→s = 4Gv→s + T 4Sv→s µ ¶ N (ze)2 1 N (ze)2 T ∂εs = −1 + 8π 0 ri εs 8π 0 ri ε2 ∂T s ¶ µ 2 N (ze) 1 T ∂εs −1 = + 2 8π 0 ri εs εs ∂T (24.From
µ
∂G ∂T
¶
P
= −S ⇒
µ
∂4Gv→s ∂T
¶
P
= −4Sv→s .9)
The only variable in the above equation that has a temperature dependence is the dielectric constant of the solvent so. µ ¶ 1 N (ze)2 ∂εs N (ze)2 ∂ .
(24. εs (24.2.8)
we ﬁnd entropy to be 4Sv→s ∂ =− ∂T " N (ze)2 8π 0 ri µ ¶# 1 −1 .

3. 4. Annihilation of defects: A small ion may be captured in a micro-cavity within the solvent releasing the energy of the micro-cavity defect. Changes in solvent structure: the local environment of the ion has a diﬀerent arrangement of solvent molecules than that of the bulk solvent. so the initial structure of the solvent must breakdown and the new structure must form. 2. The solvophobic eﬀect: a cavity must form in the solvent to accommodate the ion.1.
176
. Speciﬁc interactions: any interaction energy speciﬁc to the particular ionsolvent pair: Hydrogen bonding being the prime example.

The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.2)
. This section should not substitute for your studying of the rest of this material.1)
(25. The equations are collected here simply for handy reference for you while working the problem sets.25. 177
177
dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP
(25. Key Equations for Exam 4
Listed here are some of the key equations for Exam 4.
Equations
• Some thermodynamic relations H = U + PV A = U − TS G = H − TS • The chemical potential equation μi = μª + RT ln ai i • The 4G equation (this should be posted on your refrigerator) 4G = 4Gª + RT ln Q.

At equilibrium 4G = 0 and 4Gª = −RT ln Ka • For an ideal gas CP m = Cvm + R (25.3)

(25.4)

• The Debye—Hukel limiting Law (DHLL):

√ ln γ ± = −α |z+ z− | I.

(25.5)

• The ratio of the current carried by the cation versus the anion in terms of ion mobility is I+ u+ = (25.6) I− u− • The chemical potential equation μi = μª + RT ln ai i • The 4G equation (this should be posted on your refrigerator) 4G = 4Gª + RT ln Q. At equilibrium 4G = 0 and 4Gª = −RT ln Ka • 4G for the Born model: 4Gv→s N (ze)2 = 8π 0 rs µ ¶ 1 −1 εs (25.9) (25.8) (25.7)

(25.10)

• 4G for transfer of an ion form the β phase to the α phase, µ ¶ N (ze)2 1 1 − 4Gβ→α = 8π 0 ri εα εβ

(25.11)

178

Chemistry 352: Physical Chemistry II

179

179

Part V Quantum Mechanics and Dynamics

180

180

26. Particle in a 3D Box

We now return to quantum mechanics and investigate some of the important models that we omitted from the ﬁrst semester. In particular we will look at the particle in a box in more than one dimension. We will also solve models which deal with rotations.

**26.1. Particle in a Box
**

Recall that the important ideas from the 1D particle in a box problem were The potential, V (x), is given by ⎧ ⎪ ⎨ ⎪ ⎩ ∞ ∞ x≤0 0<x<a . x≥a

V (x) =

0

(26.1)

Because of the inﬁnities at x = 0 and x = a, we need to partition the x-axis into the three regions shown in the ﬁgure.

181

181

Now, in region I and III, where the potential is inﬁnite, the particle can never exist so, ψ must equal zero in these regions. The particle must be found only in region II. The Schrödinger equation in region II is (V (x) = 0) −~2 d2 ψ(x) ˆ Hψ = Eψ =⇒ = Eψ, 2m dx2 The general solution of this diﬀerential equation is ψ(x) = A sin kx + B cos kx, where k = q

2mE . ~2

(26.2)

(26.3)

Now ψ must be continuous for all x. Therefore it must satisfy the boundary conditions (b.c.): ψ(0) = 0 and ψ(a) = 0. From the ψ(0) = 0 b.c. we see that the constant B must be zero because cos kx|x=0 = 1. So we are left with ψ(x) = A sin kx for our wavefunction.

182

The second b.c., ψ(a) = 0, places certain restrictions on k. In particular,

nπ , n = 1, 2, 3, · · · . a The values of k are quantized. So, now we have kn = ψn (x) = A sin nπx . a

(26.4)

(26.5)

The constant A is the normalization constant. Solving for A gives A= r

2 . a

(26.6)

Thus our normalized wavefunctions for a particle in a box are (in region II) r nπx 2 sin . (26.7) ψ n (x) = a a We found the energy levels to be En =

h n2 π 2 ~2 ~= 2π n2 h2 = . 2ma2 8ma2

(26.8)

**26.2. The 3D Particle in a Box Problem
**

We now consider the three dimensional version of the problem. The potential is now V (x, y, z) = ( 0, 0 < x < a, 0 < y < b, 0 < z < c . ∞, else (26.9)

183

Now the Schrödinger equation is −~2 2 ˆ ∇ ψ = Eψ Hψ = Eψ ⇒ 2m µ ¶ −~2 ∂ 2 ψ ∂ 2 ψ ∂ 2 ψ + 2 + 2 = Eψ. ⇒ 2m ∂x2 ∂y ∂z

(26.10)

It is generally true that when the Hamiltonian is a sum of independent terms, we can write the wavefunction as a product of wavefunctions ψ(x, y, z) = ψx (x)ψ y (y)ψ z (z). (26.11)

This lets us perform a mathematical trick which is sometimes useful in solving partial diﬀerential equations. Subbing the product wavefunction into the Schrödinger equation we get µ ¶ −~2 ∂ 2 ψx ψy ψz ∂ 2 ψx ψy ψz ∂ 2 ψx ψy ψz = Eψ x ψy ψz + + (26.12) 2m ∂x2 ∂y 2 ∂z 2 µ ¶ −~2 ψy ψz ∂ 2 ψx ψx ψz ∂ 2 ψy ψx ψy ∂ 2 ψz = Eψ x ψy ψz . + + 2m ∂x2 ∂y 2 ∂z 2

We now divide both sides by ψx ψy ψz to get µ ¶ 1 ∂ 2ψy 1 ∂ 2ψz −~2 1 ∂ 2 ψx = E. + + 2m ψx ∂x2 ψy ∂y 2 ψz ∂z 2 This equation is now of the form f (x) + g(y) + h(z) = C, where C is a constant. If we take the derivative with respect to x we get d→ f (x) + g(y) + h(z) = C, dx → dC df (x) dg(y) dh(z) + + = , dx dx dx dx df (x) = 0, dx

(26.13)

(26.14)

(26.15)

184

ny Ez. Hence we immediately have ψx = ψy ψz and Ex.nx + Ey. = b b r nz πz 2 sin = c c r (26. Similarly for g(y) and h(z) Applying this to our Schrödinger equation means that we have converted our partial diﬀerential equation into three independent ordinary diﬀerential equations.So. f (x) is a constant.19)
and the total energy is (26.18) nx πx 2 sin . 8ma2 n2 h2 y = .16)
√ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex.nx = Ey.17) (26.
(26.nz The total wavefunction is n2 h2 x .ny + Ez.nz . 8mb2 n2 h2 z = . −~2 d2 ψx −~2 1 d2 ψx = Ex =⇒ = Ex ψx 2m ψx dx2 2m dx2 −~2 d2 ψy −~2 1 d2 ψy = Ey =⇒ = Ey ψy 2m ψy dy 2 2m dy 2 −~2 d2 ψz −~2 1 d2 ψz = Ez =⇒ = Ez ψz 2m ψz dz 2 2m dz 2 which we recognize as the 1D particle in a box equations.20)
185
. 8mc2 (26. a a r ny πy 2 sin .

(nx = 1. Let the 3D box be a cube (a = b = c) then the states (nx = 2. nz = 1). (26. When n(> 1) states have the same total energy they are said to be n-fold degenerate.Degeneracy The 3D particle in a box model brings up the concept of degeneracy. ny = 2. ny = 1.21)
186
. ny = 1. (nx = 1. nz = 1). nz = 2) have the same total energy and thus are degenerate.

transforms a function. Operator Algebra
We now take a mathematical excursion and discuss the algebra of operators.. into another ˆ function. • Algebra: An algebra is a speciﬁc collection of rules applied to a set of objects and a particular operation — Rules ∗ Transitivity ∗ Associativity ∗ Existence of an identity ∗ Existence of an inverse — e. Operators
27.1.. y = sin x.g. say y. etc. say O. say f . y = x2 . Deﬁnitions • Function: A function. is related to an independent variable.g. say g: Of(x) = g(x). Multiplication on the set of real numbers 187
187
. describes how a dependent variable.27. ˆ • Operator: An operator. say f. Addition on the set of real numbers. say x: y = f(x) — e.

2)
Algebraic rules for operators 1.4) (27.— Note: Commutivity is not a requirement of an algebra ∗ example 1: multiplication on the set of real number is commutive: ab = ba ∗ example 2: multiplication on the set of n × n matrices is not commutive: ab 6= ba in general..6)
188
.3)
ˆˆ ˆ α β αf (x) = β (ˆ f (x)) .5) (27. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x). then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2. e. Inverse: ˆ if αf (x) = g(x) and βg(x) = f (x) ˆ ˆ ˆ then β = α−1 and is said to be α inverse ˆ (27. ˆˆ but in general αβf (x) 6= β αf (x). " #" # " # 1 0 3 1 3 1 = (27. ˆˆ 4. Equality: ˆ if α = β.g. ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3.1) 2 1 1 1 7 3 but " 3 1 1 1 #" 1 0 2 1 # " 5 1 3 1 # " 3 1 7 3 #
=
6=
(27. Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27.

7)
189
. • x: xf(x) = xf(x) ˆ ˆ ³ ´ ¢ ¡ ˆ ˆ ˆ ˆ ˆ d • d2 : d2 f (x) = d df (x) = d dx f (x) =
d f (x) dx d dx
ˆ ˆ • d: df (x) =
• ˆ: ˆf (x. y. z) = f (−x. z) ˆ • ∇: ∂x ∂y ∂z ´ ³ 2 2 2 ∂ ∂2 ∂2 ˆ ˆ • ∇ : ∇ f (x.Linear operators: • A special and important class of operators • They obey all of the above properties in addition to — α (f (x) + g(x)) = αf (x) + αg(x). This leads to the construction of the ˆˆ ˆˆ commutator. z) = ∂ ex + ∂ ey + ∂ ez f(x. ˆ α Hermitian operators: • A special class of linear operators • All observables in quantum mechanics are associated with Hermitian operators • The eigenvalues of Hermitian operators are real Some important operators 1. −y. ◦]: h i ˆ ≡ αβ − β α. z)
¡d
dx
¢ f (x) =
d2 f (x) dx2
Commutators: We have seen that in general αβ 6= β α. where λ is a complex number. β ˆ ˆˆ ˆˆ (27. y. y. −z) ı ı ´ ³ ˆ ∇f(x. and ˆ ˆ ˆ — α(λf (x)) = λˆ f (x). y. z) = ∂x2 + ∂y2 + ∂z2 f (x. [◦. y. α.

ˆ α ˆ ˆ β (ˆ f ) = β (af) = aβf because f is an eigenfunction of α. ˆ ˆ If αf (x) = af (x) and β and α commute. ˆ ˆ The proof goes as follows: On the one hand. this to be true is if βf
190
. β = 0 and α and β are said to commute with one another. ˆˆ ˆ ˆ If αβ ˆ ˆ ˆ The eigenvalue equation: If αf (x) = g(x) and g(x) = af(x). We shall see that eigenvalues of certain operator can be identiﬁed as experimental observables.10)
ˆ because β and α commute.8)
The eigenvalue equation is of fundamental importance in quantum theory. then the operator equation. ˆ ˆ (27. Commuting operators and simultaneous sets of eigenfunctions. then α.9)
(27. ³ ´ ˆ α β (ˆ f ) = α βf ˆ ˆ ³ ´ ³ ´ ˆ α βf = a βf . ˆ On the other hand.h i ˆ = β α. The only way for ˆ ˆ = bf. then βf (x) = bf (x). ˆ Thus
(27.11)
ˆ which states that βf is an eigenfunction of α with eigenvalue a. αf (x) = g(x) ˆ ˆ becomes the eigenvalue equation αf (x) = af (x). ˆ (27.

12) j
space
Theorem 2: The eigenfunctions of a Hermitian operator form a complete set Corollary (the superposition principle): Any arbitrary function ψ in the space of eigenfunctions {ϕi } can be written as a superposition of these eigenfunctions: X ψ= ai ϕi (27. Completeness.27. and the Superposition Principle
Theorem 1: The eigenfunctions of a Hermitian operator corresponding to diﬀerent eigenvalues are orthogonal: Z ψ∗ ψk = 0.13)
i
191
. j 6= k.2. Orthogonality. (27.

28. Angular Momentum

We will encounter several diﬀerent types of angular momenta, but fortunately they are all described by a single theory Before starting with the quantum mechanical treatment of angular momentum, we ﬁrst review the classical treatment.

**28.1. Classical Theory of Angular Momentum
**

The classical angular momentum, L, is given by L=x×p (28.1)

Hence,

The vector cross-product can be computed by ﬁnding the following determinant: ¯ ¯ ¯ ex ey ez ¯ Ly Lx Lz ¯ z }| { ¯ z }| { z }| { ¯ ¯ (28.2) L = ¯ x y z ¯ = (ypz − zpy )ex + (zpx − xpz )ey + (xpy − ypx )ez ¯ ¯ ¯ px py pz ¯ Lx = (ypz − zpy ) , Ly = (zpx − xpz ) , Lz = (xpy − ypx ) . (28.3) (28.4) (28.5)

**Another quantity that we will ﬁnd useful is L2 = L · L = L2 + L2 + L2 x y z 192
**

192

(28.6)

**28.2. Quantum theory of Angular Momentum
**

So, in accordance with postulate II, we replace the classical variables with their operators. That is, µ ¶ ˆ x = (ˆpz − z py ) = ~ y ∂ − z ∂ , (28.7) L yˆ ˆˆ i ∂z ∂y µ ¶ ∂ ∂ ~ ˆ z −x , (28.8) zˆ ˆˆ Ly = (ˆpx − xpz ) = i ∂x ∂z µ ¶ ∂ ∂ ~ ˆ x −y . (28.9) xˆ ˆˆ Lz = (ˆpy − y px ) = i ∂y ∂x Recall the basic commutators. ∙ ¸ ∂ , u = 1, ∂u ∙ ¸ ∂ , v = 0, ∂u (28.10)

where u, v = x, y, or z and u 6= v. From these basic commutators one can derive h i i h ˆ ˆ ˆ ˆ ˆ x , Ly = i~Lz , ˆ y , Lz = i~Lx , L L

and

i h ˆ ˆ ˆ z , Lx = i~Ly L

(28.11)

i h i h i h ˆ ˆ ˆ ˆ ˆ ˆ 2 , Lx = L2 , Ly = L2 , Lz = 0 L

(28.12)

It is often convenient to express the angular momentum operators in spherical polar coordinates as follows. ¶ µ ∂ ∂ ˆ Lx = i~ sin φ + cot θ cos φ , (28.13) ∂θ ∂φ ¶ µ ˆ y = −i~ cos φ ∂ − cot θ sin φ ∂ , (28.14) L ∂θ ∂φ

193

∂ ˆ Lz = −i~ ∂φ µ 2 ¶ 1 ∂2 ∂ ∂ 2 2 ˆ + cot θ + L = −~ ∂θ sin2 θ ∂φ2 ∂θ2

(28.15) (28.16)

**28.3. Particle on a Ring
**

Consider a particle of mass μ conﬁned to move on a ring of radius R. The moment of inertia is I = μR2 The Hamiltonian is given by ˆ −~2 d2 L2 ˆ H= z = 2I 2I dφ2 (note that we use d rather than ∂ since the problem is one-dimensional). The Schrödinger equation becomes −~2 d2 ψ = Eψ 2I dφ2 (28.18) (28.17)

Notice that this Schrödinger equation is exactly the same form as the particle in a box. The only diﬀerence is the boundary conditions. The boundary condition for the particle in a box were ψ was zero outside the box. Now the boundary condition is that ψ(φ) = ψ(φ + 2π). The wavefunction must by 2π periodic. The allowable wavefunctions are

⎧ ⎪ A cos mφ ⎨ ψm (φ) = A sin mφ , ⎪ ⎩ Aeimφ

(28.19)

194

m = 0, ±1, ±2, ±3, . . . These wavefunctions are really the “same.” It will be most convenient to use ψm (φ) = Aeimφ as our wave functions. Plugging ψm (φ) = Aeimφ into the Schrödinger equation gives −~2 d2 Aeimφ = Em Aeimφ 2I dφ2 ~2 m2 imφ Ae = Em Aeimφ 2I Therefore the energy levels (the eigenvalues) for a particle in a ring are m2 h2 ~2 m2 = . 2I 8π2 I Next we need to ﬁnd the normalization constant, A. Z 2π ψ∗ ψdφ 1 = Z0 2π 1 = A2 e−imφ eimφ dφ 0 Z 2π 2 1 = A dφ = 2πA2 , Em =

0

(28.20)

(28.21)

(28.22)

thus

1 . 2π Hence the normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . 2π A=

r

(28.23)

(28.24)

**28.4. General Theory of Angular Momentum
**

To discuss angular momentum in a more general way it is convenient to deﬁne two so-called ‘ladder’ operators ˆ ˆ ˆ L+ ≡ Lx + iLy (28.25)

195

and ˆ ˆ We collect here the commutators of L+ and L− : h i ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ Lz , L+ = L+ ⇒ L+ Lz = Lz L+ − L+ i h ˆ ˆ ˆ ˆ ˆ ˆ ˆ ˆ Lz , L− = −L− ⇒ L− Lz = Lz L− + L− ˆ ˆ ˆ L− ≡ Lx − iLy (28.26)

(28.27) (28.28)

ˆ ˆ Now, since Lz and L2 commute there must exist a set of simultaneous eigenfunctions {ψi } ˆ (28.29) Lz ψi = mψ i and ˆ L2 ψi = k2 ψi (28.30) Physically, k~ represents the length of the angular momentum vector and m~ represents the projection onto the z-axis. (Note: for simplicity in writing we are ‘hiding’ the ~ in the wavefunctions.) On these physical grounds we conclude |m| ≤ k, i.e., k sets an upper and lower limit on m. Let’s deﬁne the maximum value of m to be a new quantum number l ≡ mmax . (Thus l ≤ k). And let’s deﬁne the minium value of m to be a new quantum number l0 ≡ mmin . (Thus −l0 ≤ k) Now, at least one of the eigenfunctions in the set {ψ i } yields the eigenvalue mmax ˆ (or l) when operated on by Lz . Let’s call that eigenfunction ψl ; ˆ Lz ψl = lψ l . ˆ Now we can operate on both sides of this equation with L− : ˆ ˆ ˆ L− Lz ψl = L− lψ l (28.32) (28.31)

196

ˆ ˆ ˆ ˆ ˆ Using the commutator relation L− Lz = Lz L− + L− we get ´ ³ ˆ ˆ ˆ ˆ Lz L− + L− ψl = lL− ψl ˆ ˆ ˆ ˆ Lz L− ψl + L− ψl = lL− ψl

(28.33)

Bringing the second term on the left hand side over to the right hand side gives ˆ ˆ ˆ ˆ Lz L− ψl = lL− ψl − L− ψl ˆ ˆ ˆ Lz L− ψl = (l − 1)L− ψl | {z } | {z }

ψ l−1 ψ l−1

(28.34)

ˆ ˆ We see that L− ψl ≡ ψl−1 is in fact an eigenfunction of Lz (with associated eigenvalue (l − 1)) and is thus a member of {ψi } . The eigenfunction ψl−1 has an associated eigenvalue that is one unit less then the maximum value. ˆ− The above procedure can be repeated n times so that Ln ψl = ψl−n provided n does not exceed l − l0 . The eigenfunction ψ l−n has an associated eigenvalue that is n units less then the maximum value, i.e., ˆ Lz ψl−n = (l − n)ψ l−n . (28.35) The largest value of n is l − l0 . For that case, ˆ Lz ψl0 = (l − l + l0 )ψl0 = l0 ψl0 . (28.36)

ˆ Similar behavior is seen for the operator L+ , except in the opposite direction–the ˆ eigenvalue is increased by one unit for each action of L+ . For example ˆ ˆ ˆ L+ Lz ψl0 = L+ l0 ψl0 ´ ³ ˆ ˆ ˆ ˆ Lz L+ − L+ ψl0 = l0 L+ ψl0 (28.37)

ˆ ˆ ˆ Lz L+ ψl0 = (l0 + 1)L+ ψl0 .

197

ˆ ˆ The raising and lowering nature of L+ and L− is why they are called ladder operators. ˆ ˆ We can not act with L+ and L− indeﬁnitely since we are limited by l–we reach the ends of the ladder. This requires that ˆ L− ψl0 = 0 (we can’t go lower than the lowest step) and ˆ L+ ψl = 0 (we can’t go higher than the highest step). ˆ ˆ ˆ ˆ Often times the ladder operators appear in tandem either as L− L+ or L+ L− so it is useful list some identities for these products ˆ ˆ ˆ ˆz ˆ L− L+ = L2 − L2 − Lz and ˆ ˆ ˆ ˆz ˆ L+ L− = L2 − L2 + Lz (28.41) (28.40) (28.39) (28.38)

We can use these identities to derive a relation between the quantum numbers k and l. We begin with ³ ´ ˆ ˆ − L+ ψl = L− L+ ψl = 0, ˆ ˆ L

(28.42)

Therefore

but from the ﬁrst of the above identities ´ ³ ˆz ˆ ˆ ˆ ˆ L− L+ ψl = L2 − L2 − Lz ψl = (k2 − l2 − l)ψ l k2 − l2 − l = 0 ⇒ k = p l(l + 1).

(28.43)

(28.44)

198

(28. l − 1. mmin = −l and so m = l. ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28. . −l.We we can also consider ³ ´ ˆ ˆ ˆ ˆ L+ L− ψl0 = L+ L− ψl0 = 0 ´ ³ ˆ ˆ ˆz ˆ ˆ L+ L− ψl0 = L2 − L2 + Lz ψl0 = (k 2 − l02 + l0 )ψl0 . l(l + 1) − l02 + l0 = 0. l − 2.48) (28. Quantum Properties of Angular Momentum
The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψlm . φ).49)
If we write out the ﬁrst of these explicitly in spherical polar coordinates as a partial diﬀerential equation we obtain 1 ∂ 2 ψlm ∂ 2 ψlm ∂ψlm + + cot θ + l(l + 1)ψ lm = 0 ∂θ sin2 θ ∂φ2 ∂θ2 (28.50)
The solutions to this partial diﬀerential equation are known to be the spherical harmonic functions ψ lm = Ylm (θ. This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer. (28. −l + 1 .46)
substituting in the relation we just found for k gives
(28. .5. simplifying gives l = −l0 Thus mmax = l.51)
199
.47)
28.45)
and
(28. . .

The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 .The spherical harmonics are functions of two variables. φ)Ylm (θ.54)
l(l + 1)h2 l(l + 1)~2 = = El .
200
. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal. φ) = APl (θ)eimφ . φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28. All 2l + 1 of these wavefunctions correspond to the same energy. ψlm = Ylm (θ.
|m| |m|
(28.55) (28. We know that there are 2l + 1 diﬀerent m values for a particular l value. meaning. They are also built-in functions of Mathematica. 2I 2I Thus Elm = (28.52)
where the Pl (θ) are the Legendra polynomials and A is normalization constant.53) Yl∗m0 (θ. 2I so the Schrödinger equation is ~2 ˆ ~2 ˆ Hψ lm = Elm ψlm ⇒ L2 ψlm = Elm ψlm ⇒ l(l + 1)ψlm = Elm ψlm .1. In other words.56) 2I 8π2 I There is no m dependence for the energy. Both the spherical harmonics and the Legendra polynomials are tabulated. ( Z 2π Z π 1 l0 = l and m0 = m (28.5. but they are a product of a function only of θ and a function only of φ. We say the there is a 2l + 1 degeneracy of the energy levels. (28. the energy levels are determined only by the value of l.

29.1) and ψ s (θ) = ψs (θ + 4π). Spin Angular Momentum
We learned above that l may take on integer or half-integer values. The values of m = ms are limited to +1/2 and −1/2. Systems in which l takes on half-integer values are peculiar. One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π antiperiodic): ψs (θ) = −ψs (θ + 2π) (29. l = s = 1/2.2)
That means that the system has to ‘rotate’ twice (in spin space not coordinate space) to get back to its original state. One example of such a system is the spin of an electron. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗
201
201
.1. (29. These systems have no classical analogs. Addition of Angular Momentum
29.

however.29. we use J when we speak generally. LS coupling (also called Russell-Saunders coupling) • works well for low atomic weight atoms (ﬁrst couple of rows of the periodic table) P • ﬁnd the total spin angular momentum S = Ms. (Ms = i msi ) P • ﬁnd the total orbital angular momentum L = Mmax . The electrons in many electron atoms couple. 29. • we will not use this method. jj coupling • applies to higher atomic weight atoms • ﬁnd subtotal angular momentum for each electron ji = li + si P • then ﬁnd total angular momentum by J = i ji .2.2. the total angular momentum. The Addition of Angular Momentum: General Theory Consider two sources of angular momentum for a system represented by the opˆ ˆ ˆ ˆ ˆ ˆ ˆ erators J1 and J2 (J1 and J2 could be L or S angular momentum. J.max . Addition of Angular Momentum
In atoms the are a number of sources of angular momentum: The l’s and s’s of each of the electrons.)
202
. 1.1. One measures. (M = i mi ) • then J = L + S 2. The are two main coupling schemes which account for the total angular momentum of the atom.

Jmin = |j1 − j2 | . 29. . Thus the allowed values of J are J = j1 + j2 . The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29. (29.2. .ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 . |j1 − j2 | + 1. ˆ ˆ ˆ The total z-component of the angular momentum is JzT = Jz1 + Jz2 The last statement implies that the orientation quantum number of the total system is simple the sum of that for the components M = m1 + m2 (29.5)
The total angular momentum is quantized is exactly the same manner as any other angular momentum. |j1 − j2 | . .2.3)
We need to determine the allowed values of the total angular momentum quantum number J.4)
This corresponds to a situation in which component angular momentums add in the most favorable manner The minimum value of J is determined by the case when the components add in the least favorable manner. That is.6)
203
. . j1 + j2 − 1. An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29.

In general the term symbol is simply notates the total orbital angular momentum and spin degeneracies of a particular set of states (or a state in the case of a singlet state).3. Term symbols are simply shorthand notion used to identify states. it is worthwhile to brieﬂy discuss them.spin state α(1)α(2) β(1)β(2) α(1)β(2) + β(1)α(2) α(1)β(2) − β(1)α(2)
ms1
1 2
ms1
1 2
MS 1 −1 0 0
S 1 1 1 0
−1 2 0 0
−1 2 0 0
Counting states: The spin degeneracy.2. those being 1 S and 3 S during our discussion of helium. L 0 symbol S 1 P 2 D 3 F 4 5 . Term symbols are useful for predict and understanding spectroscopic data. Term Symbols We have already seen several term symbols. In the above example the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states. The orbital degeneracy is given by gL = 2L + 1. of the states is given by 2S + 1. So. G H
204
. For historical reasons L values are associated with a letter like the l values of a hydrogenic system are. 29. gS .

p1 and p5 have the same term symbol. If several terms have the same multiplicity then ground state will be that of the largest L.g.7)
205
. Rules: 1. Many electron atoms have term symbols associated with their states. Highest J value (inverted) “hole” 29. Spin Orbit Coupling A charge possessing angular momentum has a magnetic dipole associated with it. 3.2. The ground state will have maximum multiplicity. 1.4. An electron and a “hole” lead to equivalent term symbols. The spin—orbit Hamiltonian is [ ˆ HSO = hcAL · S ´ ³ ˆ ˆ ˆ ˆ SO = hcA J 2 − L2 − S 2 .. • E. These dipoles interact with a certain spin—orbit interaction energy ESO . 3. S = 0. notated by 1 S 2.The term symbol for a particular states is constructed from the following general template gS LJ . 2. All closed shells have zero spin and orbital angular momentums: L = 0. Hund’s Rule for the ground state only. H 2 (29. An electron has orbital and spin magnetic dipoles. These states are all singlet S states. Lowest J value (regular) “electron”.

where A is the spin—orbit coupling constant.8)
206
. From the Hamiltonian the spin—orbit interaction energy is ESO = hcA [J(J + 1) − L(L + 1) − S(S + 1)] 2 (29.

we always took the simplest approximation to give the qualitative properties of the unsolvable system.1. Approximation Techniques
As we learned last semester. Last semester. Now we will consider two important quantitative approximation methods: (i) perturbation theory and (ii) variational theory
30. Consequently we must be satisﬁed with using approximation methods.30.
207
207
. • Treat the diﬀerence between the two systems as a perturbation to the solvable system • Use the solvable system’s wavefunctions as a zeroth order approximation to the wavefunctions for the unsolvable system. • These wavefunctions are used to ﬁnd a ﬁrst order correction to the energy. Perturbation Theory
The basic procedure of perturbation theory • Find a solvable system that is similar to the system at hand. there are very few models for which we can obtain an exact solution.

This is given by Z (1) ˆ En = ψ(0)∗ H (1) ψ(0) dx.4)
208
. • The procedure is repeated to get higher and higher order approximations.1)
(1)
where En is the nth state energy for the unperturbed (solvable) system and En is the ﬁrst order correction. (0)
(30. Example: the quartic oscillator • Consider the quartic oscillator described by the potential V (x) = 1 kx2 +ax4 2 where a is very small and can be treated as a perturbation. .
√ 2 This has energy levels En = ~ω(n+ 1 ) and wavefunctions An Hn ( αx)e−αx /2 .3)
• The perturbative part of the Hamiltonian is ˆ H (1) = ax4 . (30. 2 q where α = km ~ (30. This process get algebraically intensive so we will only go as far as listing the ﬁrst order energy correction.• The ﬁrst order energy is then used to make a ﬁrst order approximation to the wavefunction. . H=− 2 2m dx 2 (30. . • The obvious solvable system is the harmonic oscillator: 1 ~2 d2 ˆ + kx2 .2) n n
all space
ˆ where H (1) is the ﬁrst order correction to the Hamiltonian–the perturbation. The nth state energy in perturbation theory:
(0) (1) En = En + En + .

6)
all space
The trial energy is now a function of the adjustable parameter. The value of the parameter which minimizes the energy. The basis for this is the variation theorem which states Etrial ≥ E. The trial energy is calculated by Etrial = R R
all space
ˆ ψ∗ Hψtrial dx trial ψ∗ ψtrial dx trial (30.• For example. p. We will not prove this theorem here. gives a trial wavefunction which is closest to the real wavefunction.2. 5 2 2 4α
30.5) E0 = −∞ Z ∞ 2 2 A0 e−αx /2 ax4 A0 e−αx /2 dx = −∞ Z ∞ 2 2 x4 e−αx dx = aA0 √ −∞ 3 πaA2 0 = . that we use to minimize the trial energy by setting dEtrial =0 dp (30. the ground state energy correction is then calculation from Z ∞ (1) (0)∗ ˆ (0) ψ0 H (1) ψ0 dx (30. Variational method
The basic idea behind the variational method is to use a trial wavefunction with an adjustable parameter. 5 4α 2 so the ﬁrst order ground state energy for a quartic oscillator is √ ~ω 3 πaA2 0 + E0 ' .7)
209
. Etrial .

)
210
. but with reasonably good trial functions one is pretty safe in having a minimum. (Strictly speaking we should check that we have a minimum and not a maximum or inﬂection point.and solving for p.

ﬁring an electron down a particle accelerator. The spin system discussed above is an example of a two level system.1. Unlike the harmonic oscillator it has no classical analogue. the two level system is a close second. The Two Level System and Quantum Dynamics
Our entire discussion of quantum mechanics thus far had dealt only with time independent quantum mechanics. The Two Level System
If the harmonic oscillator is the most important model in all a physics. For example. The two level system is inherently quantum mechanical in nature.31. Obviously there are cases where quantum objects move with time. but ﬁrst we will discuss the very important model of the two level system.
211
211
. We shall ﬁnally get to quantum dynamics in this chapter. The time variable never appears in any expression.
31.

ˆ H=
1 δ 1.Consequently.
212
. we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators.
(31. i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian.2)
where δ j.°
+ 2 δ 2. j 6= k (31.1)
TLS
R where TLS dΩ means integration over the two level space (which is really just the P sum 2 ).° .° “projects out” the j th state of the wavefunction being acted on. The two level system consists of two states ψ1 and ψ2 separated by energy 4 = 2 − 1 as shown below
The states ψ1 and ψ2 are orthonormal: Z ψ∗ ψk dΩ = j ( 1 0 j=k .

then ˆ Hψ = ( 1 δ 1.7)
213
.° ) (aψ 1
+ bψ2 )
2 δ 2.° 2 δ 2.6)
(31.4)
(31. 2 2 (31.For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 .°
(31.
We can invert above equations and solve for ψ1 and ψ2 in terms of ψL and ψR 1 1 ψ1 = √ ψL + √ ψR 2 2 and 1 1 ψ2 = √ ψL − √ ψR .5)
states.3)
(aψ1 + bψ2 ) +
(aψ1 + bψ2 )
= a 1 ψ1 + b 2ψ2 Another orthonormal set of wavefunctions are the so-called ‘left’ 1 1 ψL = √ ψ1 + √ ψ2 2 2 and ‘right’ 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31.° + =
1 δ 1.

What has been kept hidden up to now is the fact that the eigenfunctions are really multiplied by a phase factor of the form . t)dx¯ (31.10)
Does this mean the eigenstates are not stationary states? To determine this we need to calculate the probability of ﬁnding the particle in the same eigenstate at some future time. t) ∂t i ∂ψn (x)e− ~ En t i~ ∂t i ∂e− ~ En t i~ψ n (x) ¶ ∂t µ i i i~ψ n (x) − En e− ~ En t ~ i~
i
ˆ = HΨn (x. t) = ¯ Ψn (x. t)
i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i
(31.11) ¯ ¯ ¯2 ¯Z ¯ ¯ i ∗ − ~ En t dx¯ = ¯ ψ n (x)ψ n (x)e ¯ ¯ ¯ ¯2 Z ¯ −iE t ¯ ∗ ¯e ~ n ψn (x)ψ n (x)dx¯ = ¯ ¯ ¯ i ¯2 ¯ ¯ = ¯e− ~ En t (1)¯ = 1. t) ≡ ψn (x)e− ~ En t
i
(31. Quantum Dynamics
So far we have been concerned with the eigenfunctions and eigenvalues (energy levels) of the various quantum systems that we have discussed. 0)Ψn (x. Ψn (x.2.8)
We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x.9)
ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x)
(31.
214
.31.

t) = ¯ ¯ ¯Z µ ¶¯2 ¶µ ¯ ¯ i i 1 ∗ 1 ∗ 1 1 − ~ E1 t − ~ E2 t ¯ ¯ √ ψ1 (x) + √ ψ2 (x) √ ψ1 (x)e = ¯ + √ ψ2 (x)e ¯ 2 2 2 2 ¯ Z Ã ! ¯2 i i ¯ ¯1 ψ ∗ (x)ψ 1 (x)e− ~ E1 t + ψ∗ (x)ψ 2 (x)e− ~ E2 t ¯ ¯ 1 1 dx¯ . The “left” and “right” wavefunctions that we saw in the discussion of the two level system are examples of superposition states.12)
(31. it may be in a superposition of any number of eigenstates.14) i i ∗ ∗ − ~ E1 t − ~ E2 t ¯ ¯2 +ψ2 (x)ψ 1 (x)e + ψ2 (x)ψ 2 (x)e The “cross-terms” (those of the form ψ∗ (x)ψ 2 (x) and ψ ∗ (x)ψ 1 (x)) are zero when 1 2
215
. As an example consider the state 1 1 Φ(x.so no matter what time t we check we will always ﬁnd the system in the same eigenstate. The phase factor does become important for superposition states. In general the state of the system need not be in one particular eigenstate. t) + √ Ψ2 (x. t) 2 2 exposing the phase factors we get
i i 1 1 Φ(x. Thus the eigenstates are stationary states. t)¯ P (x. 0)Φ(x. t) = √ Ψ1 (x. Similar to before we calculate ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x. = ¯ (31. t) = √ ψ1 (x)e− ~ E1 t + √ ψ2 (x)e− ~ E2 t 2 2
(31.13)
Let’s now track the probability of ﬁnding the particle in the same superposition state.

t)¯ (31.15) P (x. 0)Φ(x. t) = ¯ ¯ ¯ Z ³ ´ ¯2 ¯ ¯1 i i ∗ ∗ − ~ E1 t − ~ E2 t dx¯ ψ 1 (x)ψ 1 (x)e + ψ2 (x)ψ 2 (x)e = ¯ ¯ ¯2 ¯ µ ¶¯2 Z Z ¯1 − i E t ¯ i ∗ ∗ − ~ E2 t 1 ¯ e ~ ψ1 (x)ψ 1 (x)dx + e ψ2 (x)ψ 2 (x)dx ¯ = ¯ ¯ 2 ¯ ³ ´¯2 ´³ i ´ ³ i ¯1 − i E t ¯ i i i ¯ e ~ 1 + e− ~ E2 t ¯ = 1 e+ ~ E1 t + e+ ~ E2 t e− ~ E1 t + e− ~ E2 t = ¯ ¯ 2 4 ¶ ³ ´ 1µ i i (E1 − E2 ) 1 + ~ (E1 −E2 )t − ~ (E1 −E2 )t 1+e 1 + cos t .
216
. This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x.integrated because the eigenfunctions are orthogonal. +e +1 = = 4 2 ~ The probability of ﬁnd in the system in its original superposition states is not one for all times t.

sZ N=
space
|ψunnorm (x. This section should not substitute for your studying of the rest of this material. y. z)|2 dxdydz.18)
217
217
. ˆ hˆ i = α
space
(31.17)
• How to get the average value for some property. N unnorm (31. The equations are collected here simply for handy reference for you while working the problem sets.Key Equations for Exam 1
Listed here are some of the key equations for Exam 1.16)
• The normalized wavefunction: ψnorm = 1 ψ . The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. Z ψ∗ αψdxdydz.
(31.
Equations
• The short cut for getting the normalization constant .

8ma2 8mb2 8mc (
(31.24) L L L and h i h i h i ˆ 2 . Lx = L2 . 2I 8π2 I (31. Enx . ˆ z . Lz = i~Lx . ˆ y .
j=k .nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2. Lx = i~Ly (31. 0. Lz = 0. √ ny πy nz πz nx πx 2 2 sin sin . j 6= k
(31.27)
218
. Ly = i~Lz .26)
• The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box.• The Laplacian
∇ =
2
µ
∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z
¶
.20)
(31. ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . Ly = L2 .25)
• The energy levels for a particle in a ring are Em =
(31.
(31.19)
• Normalized wavefunctions for the 3D particle in a box.ny .22)
• Superpostion:
ψ=
X
i
ai ϕi
(31.23)
• Commonly used comutators of the angular momentum operators are h i i i h h ˆ ˆ ˆ ˆ ˆ ˆ ˆ x . 2π (31.21)
ψ∗ ψk j
=
space
1.

ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 .35)
219
.34)
(31. t) ≡ ψn (x)e− ~ En t
i
(31.30)
(31.32)
• In general
Ψn (x.33)
• The left and right superposition states are 1 1 ψL = √ ψ1 + √ ψ2 2 2 and 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31.• The eigenfunctions of angular momentum are entirely speciﬁed by two quantum numbers l and m: ψ lm .31)
• The trial energy in variation theory is calculated by R ∗ ˆ all ψ trial Hψ trial dx space Etrial = R ∗ all ψ trial ψ trial dx
space
(31. 2I (31. En = n n
all space
(31. • The ﬁrst order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx.28)
• Degeneracy for general angular momentum is gJ = 2J + 1.29) ˆ Lz ψlm = mψ lm (31.

Part VI Symmetry and Spectroscopy
220
220
.

• The mathematical properties of all the possible groups have been worked out • These mathematical properties translate into a wide variety of variety of physical properties including — Bonding — Properties of wavefunctions — Vibrational modes — Many more applications
221
221
. we will • determine the symmetry of a particular molecule.32. As far as we are concerned. Symmetry and Group Theory
We now take a short break from physical chemistry to discuss ideas from the mathematical ﬁeld of group theory. • The types of symmetry it has will determine to which symmetry group it belongs. Inherent to group theory is symmetry.

We have seen two such operators in ˆ and σ h .32.1. This type of operator arrises in the treatment of extended crystal structures. It is a set of objects and a single operation. The group is associative (but not necessarily communative) with respect to the operation. That is. For molecules we will be dealing with point group symmetry operators. 2.1) This implies ˆ Oψ = ±ψ. (32. 1. An identity element exits and is a member of the group
222
. ∗ ∗ ∗ See Handout on Symmetry Elements ∗ ∗∗ (32.2. Symmetry Operators
Any operator that leaves |ψ|2 invariant are symmetry operators for that particular system: ˆ O |ψ|2 = |ψ|2 . Mathematical Groups
In mathematics the term “group” has special meaning. These operators deal with symmetry about the center of mass. which has the following properties. the eigenvalues for the particular symmetry operator are 1 or −1. ı ˆ An example of symmetry operator that is not a point group symmetry operator would be an operator that performed some sort of translation in space.2)
32.

Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E. Water is an example of a molecule described by this point group. The multiplication table for the C2v group is C2v ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ E ˆ E ˆ C2 σv ˆ σ 0v ˆ ˆ C2 ˆ C2 ˆ E σ 0v ˆ σv ˆ σv ˆ σv ˆ σ 0v ˆ ˆ E ˆ C2 σ 0v ˆ σ 0v ˆ σv ˆ ˆ C2 ˆ E
32.
223
.3. σ v (in-plane) and σ 0v ˆ (transverse). 32. Symmetry of Functions
In the absence of degeneracy.2. for any member of the group one can ﬁnd another member of the group which.1. the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group. 4. The “product” of any two members of the group yield a member of the group.
∗ ∗ ∗ See Handout on Naming Point Groups ∗ ∗∗ ∗ ∗ ∗ See Handout on Assigning Point Groups ∗ ∗∗ Associated with a given group is a “multiplication” table.” yields the identity element. The inverse of every member of the group is also in the group.3. In other words. C2 . upon “multiplication.

ˆ • The ﬁrst value has to be +1 since the only eigenvalue of E is 1 ˆ • The eigenvalue of C2 can be +1 or −1 — When it is +1 the vectors are labelled A — When it is −1 the vectors are labelled B • The eigenvalue of σ v can be either +1 or −1 ˆ — When it is +1 the vectors are labelled with a subscript 1 — When it is −1 the vectors are labelled with a subscript 2 • The eigenvalue of σ 0v can be either +1 or −1 ˆ • Finally there is a restriction do to the fact that the eigenvalues must obey the group multiplication table. −1. As it turns out there is four possible sets of eigenvalues–hence four diﬀerent vectors: A1 = (1. 1. To see where these four vectors come from. −1. −1. In this case one can collect the eigenvalues (either +1 or −1) for each of the four symmetry operators as a four component vector. 1. −1.Connecting with the C2v group example lets consider the wavefunctions for water. ˆ — This restriction forces the eigenvalues of σv and σ 0v to be the same for ˆ the A type vectors and opposite for the B type vectors. 1) A2 = (1. 1.
224
. 1). −1) B2 = (1. −1) B1 = (1. consider the following. 1.

−1) ⊗ (1. x3 . . .4) (32.) ⊗ (y1 . . y3 . . 1. 1) = (1. . x3 y3 . . These vectors make up the : C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ
1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1
∗ ∗ ∗ See Handout on Character Tables ∗ ∗∗ 32.3)
32.
225
.The above considerations leave four vectors. In fact.) = (x1 y1 . −1.3. . −1. .1. −1. y2 . Direct Products The direct product of a two vectors is deﬁned as (x1 . the vectors represent what is call an irreducible representation of the group. .4. x2 . 1. Symmetry Breaking and Crystal Field Splitting
We shall investigate how degeneracies of energy levels are broken as one reduces the overall symmetry of the system. −1. −1) = A2 (32. there will always be the same number of vectors as symmetry elements.) For the example of the C2v group consider B1 ⊗ B2 = (1. Altogether. x2 y2 .

The degeneracies of these vectors are 1 for S. In this case there is complete rotational symmetry. 3 for P. The S vector has the symmetry of a sphere (x2 + y 2 + z 2 ) and hence is totally symmetric. nondegenerate in the octahedral case.) This is the group associated with the particle on a sphere model and the angular part of the hydrogen atom. of course. Mirror symmetry will not be considered (although in real applications one must consider all symmetry). Thus the symmetry group is the spherical group (see character table handout. The vectors are the labeled according to the angular momentum quantum numbers S. for simplicity. The P vector is triply degenerate and has the symmetry of x. When moving to octahedral symmetry we now must look at the character table for such a case–the O group (remember we are considering only proper rotations). First consider a free atom.
226
. Now consider the free atom being placed in a crystal lattice of octahedral symmetry. In the octahedral crystal the degeneracy remains in tact and these states are represented by the T1 group. D. 5 for D and so on as is familiar to us already. F. etc. P. For example placed at the center of a cube which has other atoms at the centers of each face of the cube. It is also nondegenerate so it will be.In doing this we will. consider only proper rotations (Cn ). y and z as we see from the character table for the spherical group. It remains totally symmetric so it is now represented by the vector A1 .

Now the A1 vector of the O group becomes the A1 vector of the D4 group. z(x2 − y 2 ). yz. xy. The E states from the O group become a A1 type state and a B1 type state. The remaining four atoms remain in place. This breaks the octahedral symmetry and the system now assumes D4 symmetry. The T2 states from the O group become a B2 and a E type state. Lets say that two atoms on opposite sides of the cube are moved slightly inward. The T1 states from the O group become a A2 type state and a E type state. In an octahedral environment the states split with one becoming A2 . x2 − y 2 . xz 2 . The triply degenerate T1 vector splits into a A2 state and a doubly degenerate E state.
227
. xyz. yz 2 . The F states have a degeneracy of 7 and the symmetry of z 3 . three becoming T1 and three becoming T2 . This is not readily apparent from the character tables so one needs to inspect a little harder to see it (see homework).The D vector has a degeneracy of ﬁve and the symmetry of 2z 2 − x2 − y 2 . x(x2 − 3y 2 ) and y(3x2 − y 2 ). The octahedral group is still highly symmetric. xz. Looking at the table for the O group we see the degeneracy splits: two states become E type and the remaining three become T2 type.

in this chapter we simply investigate some of the speciﬁc details regarding polyatomic molecules. With polyatomic molecules one needs to specify the coordinates of N nuclei rather than just two nuclei.
228
228
. Molecular Vibrations
As for diatomic molecules. One must now consider two diﬀerent types of polyatomic molecules: Linear and Nonlinear.33.1. To do so we begin with the 3N nuclear degrees of freedom. • For linear molecules there are 2 rotational degrees of freedom • For nonlinear molecules there are 3 rotational degrees of freedom This now leaves one with 3N − 5 vibrational degrees of freedom for linear polyatomic molecules and 3N − 6 vibrational degrees of freedom for nonlinear molecules.
33. So. As for the diatomic case 3 degrees of freedom determine the center of mass motion. Molecules and Symmetry
From our chapter on diatomic molecules last semester we have learned a great deal which caries over directly to polyatomic molecules. That leaves us with 3N − 3 coordinates to specify. it is convenient to work with center of mass coordinates.

however. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ
1 1 1 1 1 1 −1 −1 1 −1 1 −1 1 −1 −1 1
Water has three nuclei and it is nonlinear so it has 3(3) − 6 = 3 normal modes. At low energies the normal modes are well approximated as harmonic oscillators.1. Regardless of what type of vibrational motion is taking place. The number of normal modes equals the number of vibrational degrees of freedom. The three modes are the bending vibration.1. that motion is some linear combination of fundamental vibrational motions called normal modes.
33. One example was the “left” and “right” states of the two level system.1. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. Normal Modes and Group Theory The symmetry of the normal modes are associated with entries in the character table of the point group of any particular polyatomic molecule. the symmetric stretching vibration and the asymmetric stretch.2.
229
.33. Normal Modes Polyatomic molecules can undergo very complicated vibrational motion. Example: Water The point group symmetry of the water molecule is C2v .

For the bending mode. It too is associated with A1 . Consequently the bending mode is associated with A1 The same is true for the symmetric stretching mode. the vibration is complete unchanged by any of the symmetry elements.The normal modes are associated with a particular vector (row) of the character table by considering the action of the each of the symmetry elements on the normal mode. is associated with B1 since C2 and σ0v transform ˆ the mode into its opposite and σ v leaves it unchanged. however. ˆ
230
. ˆ The asymmetric stretch.

The typical “energies” for IR absorption are from 400 to 4000 cm−1 . the character tables can be used to determine IR and Raman spectra and selection rules for polyatomic molecules
34.1)
.1. The electric dipole approximation • Molecule is viewed as a collection of charges • Multipole expansion monopole + dipole + quadrapole+ · · · 231
231
(34. IR Spectroscopy
IR absorption is exactly the same as regular electronic absorption except the frequency of the electromagnetic radiation is much less. Vibrational Spectroscopy and Group Theory
We now investigate how group theory and. As for electronic absorption one typically employs the electric dipole approximation. in particular.34. This is in the Infrared region of the electromagnetic spectrum.

2)
1 1 1 1 z. μz = qz. x2 . z 2 1 1 −1 −1 xy 1 −1 1 −1 x. or z for the particular group.
232
. μy = qy. The electric dipole is μ = μx ex + μy ey + μz ez where μx = qx. The upshot of all this is as far as group theory is concerned is the following selection rule: • The vibrational coordinates for an IR active transition must have the same symmetry as either x. yz
The last column describes the symmetry of several important functions for the point group. it must be able to couple to a changing (oscillating) electric dipole. Example: Water Recall that the point group symmetry of the water molecule is C2v . xz 1 −1 −1 1 y. In order for absorption of the electromagnetic radiation to take place.• Light—matter interaction is dominated by the light—dipole coupling so the other interactions are ignored. y. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ Functions (34. We now need a column of the character table which we have ignored up to this point. y 2 .

The A2 mode is IR forbidden and any vibrations having this symmetry will not appear in the IR spectrum (or it may appear as a very weak line). B1 . So we can see immediately that the IR active modes of any molecule having this point group will be A1 . Unlike IR absorption which is based on the electric dipole. y. From before we know the modes of water have A1.2. and z. The light loses energy to the material in an amount equal to the vibrational energy of the molecules is the sample. and B1 symmetry and hence are all IR active and appear in the IR spectrum
34. Raman Spectroscopy
Raman spectroscopy is somewhat diﬀerent than IR spectroscopy in that vibrational frequencies are measured by way of inelastic scattering of high frequency (usually visible) light. Raman scattering is based on the polarizability of the molecule Roughly speaking the polarizability of a molecule determines how the electron density is distorted through interaction with an electromagnetic ﬁeld.Among these functions are x.
233
. This lose of energy shows up in the scattered light as a new down shifted frequency from that of the original input light frequency. and B2 .

The molecular quantity of interest is the polarizability tensor. We will not get into tensors in this course except to say the polarizability tensor elements are proportional to the quadratic functions. (or any combinations thereof). z 2 . y 2 . α. xz. xy. all modes are Raman active Rule of Mutual exclusion • Vibrational mode can be both IR and Raman active or inactive • If.
↔
234
. One can now inspect the character table to determine which modes will be Raman active. the molecule has inversion symmetry (contains ˆ as a symmetry ı element) then no modes will be both IR and Raman active. x2 . yz. For the example of water. however.

It is common to deﬁne Be ≡ as the rotational constant. φ).5)
(35. under the Born-Oppenheimer approximation. Recall also the Kinetic energy operator for the nuclei in the center of mass coordinates 2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN = − ~ ∇2 = − ~ ˆN T + J .3)
This is the so-called rigid rotor energy. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235
235
h 8π 2 I
(35.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part. Molecular Rotations
Recall that the three degrees of freedom that described the position of the nuclei about the center of mass were (R. We now turn our attention to the angular components to describe rotations. 2I Now. ~2 ˆ2 (35. For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 .2) J .6)
. θ. = 2μR2 8π 2 I (35.4)
(35.35. (35. R is a parameter. The R was involved in vibrations.

a rotational transition can accompany a vibrational transition.7) 2 where αe is an empirical rotational—vibrational interaction constant.
35. • One deﬁnes a rotational interaction constant that depends on the vibrational level. 2.
236
. • This is corrected for by the term −J 2 (J + 1)2 Dc .2. n. ¶ µ 1 Bn ≡ Be − n + αe . Vibrational state dependence: • The R value is dependent on the particular vibrational level. Centrifugal stretching: • Rotation tends to stretch the diatomic distance R. (35.9)
is the centrifugal stretching constant. In either case the selection rule for the transition is 4J = ±1. There are two corrections we will now make 1. Relaxing the rigid rotor
Of course the rigid rotor is not a perfectly correct model for a diatomic molecule.35.1. This is called a pure rotational transition. Rotational Spectroscopy
A rotational transition can occur in the same vibrational level n.8)
(35. where Dc ≡
3 4Be ω2 ˜e
(35. Alternatively.

kT.3. ∗ ∗ ∗ See Handout ∗ ∗∗
35. I = Ixx + Iyy + Izz The Hamiltonian in the principle axes system is # " ˆ2 ˆ2 ˆ2 Jy ~2 Jx Jz ˆ + + H= 2 Ixx Iyy Izz
(35. The total moment of inertia. Thermal energy. The principle axes coordinate system is the one in which the z-axis is taken to be along the principle symmetry axis. ∗ ∗ ∗ See Handout ∗ ∗∗ The selection rules and the thermalized states combine to yield a multi-peaked ro-vibrational spectrum.10)
237
. at room temperature is about 200 cm−1 . Rotation of Polyatomic Molecules
There are a few additional details regarding rotations for polyatomic molecules as compared to diatomics Of course one could set-up an arbitrary center of mass coordinate system. But one system is special–the principle axes coordinate system. This means that at room temperature the many excited rotational states are populated.It turns out that typical rotational energy gaps are on the order of a few wavenumbers or less.

12)
~2 ˆ2 ˆ J H= 2Ixx
(35..17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis
238
. Linear (e. carbon dioxide) • Izz = 0.. (35.16) 8π 2 Izz h (35.14)
• The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 . Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1). benzene) • Ixx = Iyy h 8π2 Ixx (35.There are four classes of polyatomic molecules regarding rotations 1. where B= 2.g.11)
(35. Symmetric tops (e. where A= (35.g.13)
ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is # " ˆ2 ˆ2 ˆ2 ~2 Jx + Jy Jz ˆ + H= 2 Ixx Izz
(35.15)
h .

18)
(35.20)
4.g. Asymmetric tops • Ixx 6= Iyy 6= Izz • These are more complicated and we will not discuss them in detail
239
. where B= h 8π2 Ixx (35. Spherical tops (e.. methane) • Ixx = Iyy = Izz
ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1).19) ~2 ˆ2 ˆ J H= 2Ixx (35.3.

Ee as a function of R describe the eﬀective potential for the nuclei. R.1.36.
36. Molecular spectra. The Structure of the Electronic State
Last semester we saw that under the Born—Oppenheimer approximation we were able to write the molecular wavefunction as a product of an electronic part and a nuclear part. It had a qualitative shape similar to the Morse potential. Atomic spectra consist of single sharp lines due to transitions between energy levels. was parameterized by the internuclear distance. have numerous lines (bands) due to the fact that electronic transitions are accompanied by vibrational and rotational transitions. Electronic Spectroscopy of Molecules
The electronic spectra of molecules are quite diﬀerent than that of atoms. on the other hand. We found that in doing so the electronic energy level. Ee .
240
240
.

In the ﬁgure below the ground and ﬁrst excited electronic levels (as a function of R) are shown. Absorption Spectra In absorption spectroscopy.2. light demotes an electron from the ground vibrational state of the excited electronic state to any one of a number of excited vibrational levels in the ground electronic state. Note: The potential minima are not at the same value of R for each of the electronic states. ∗ ∗ ∗ See Spectroscopy Supplement p1 ∗ ∗∗ 36. light promotes an electron from the ground electronic state (and usually from the ground vibrational state too) to the excited electronic state and any of the excited vibrational states of the excited electronic state.1.1. Emission Spectra In emission spectroscopy.1.
36.
241
.

the process of is taking place. • This process is called • The molecule than emits a photon to drop back down into an excited vibrational state of the ground electronic state. ∗ ∗ ∗ See Spectroscopy Supplement p3 ∗ ∗∗ As seen in the supplement the ﬂuorescence spectrum is shifted to lower energies (red shifted) from the absorption spectrum. This is known as the Stokes shift.3. Fluorescence Spectra All during the process of absorption.∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗ 36. • This requires a lower energy (or “more red”) photon.1. Hence the Stokes shift. The main stream explanation for the stokes shift is as follows • Light promotes the system from the ground vibrational and ground electronic state to excited vibrational levels in the excited electronic state. • The system then very rapidly (on the order of tens to hundreds of femtoseconds) relaxes to the ground vibrational state of the excited electronic state.
242
.

1.2.36. The Franck—Condon principle states that the nuclei do not move during an electronic transition.i ψvib. The Franck—Condon principle When the Born—Oppenheimer approximation is applied to spectroscopic transitions.
36.i ¯ . Mathematically this means that the strength of a transition from Ψi = ψel.f is given by ¯Z ¯ ¯ ¯ ¯ ¯2 ¯Z ¯ ¯ ¯ ¯ Ψ∗ μel Ψi ¯ = ¯ ˆ f ¯ ¯ Z ¯2 ¯ ¯ ψ∗ ψ∗ μel ψel. but we will ingore this). This is down by evaulating the Franck—Condon integral.i → Ψf = ψel.f vib.1)
all space
el space
vib space
243
. Assuming the electronic transition is allowed one must calculate the probability of the vibrational transistion as well. one obtains the Franck—Condon principle.i ψvib.f ψvib. ˆ el. Physically this means that for a particular transition to be Franck—Condon active there must be good overlap of the vibrational wavefunctions involved in the transition. Franck—Condon activity
We have seen than an electronic tranistion involves not only a change in the electronic state but also in the vibrational state in general (and in the rotaitonal state as well.f ¯ (36.2.

f ψvib. (36.2) ¯ ¯ ¯ vib ¯ ¯ el space space | {z }| {z }
if 6=0.i ¯ .where μel is the electronic transition dipole. We can separate the integrals as ˆ ¯2 ¯Z ¯2 ¯Z ¯¯ ¯ ¯ ¯¯ ¯ ¯ ∗ ∗ ψel.i ¯ ¯ ˆ ψvib. allowed Franck—Condon
244
.f μel ψel.

if the signal decays slowly it will have a narrow spectrum. Spectroscopic data is obtained either in the time domain or in the frequency domain and one should readily be able to look at data in one domain and know what is happening in the other domain. One should be familiar with qualitative aspects of this time—frequency relation. The mathematics which governs these qualitative statements is Fourier transform theory which we now review. in this work. conversely. and is given by Z ∞ ˜(ω) = = [f (t)] = f f(t)eiωt dt.1)
−∞
245
245
. such as if a signal oscillates in time it will have a peak in it frequency spectrum at the frequency with which it is oscillating. =. f (ω). The Fourier transformation
The Fourier transformation. of a function f (t) will.37. if the signal decays rapidly it will have a broad spectrum and. (37.
37.1. Fourier Transforms
As a spectroscopist it is imperative to have a deep understanding of the relationship between time and frequency. Furthermore. by denoted ˜ by a tilde.

.e. Other authors use diﬀerent conventions. = [f (t)] = f (ω).2) f(ω)e−iωt dω. so one must take care to know exactly which convention is being used.e.The Fourier transformation is unique and it has a unique inverse. = f(ω) = f(t). For simplicity the symbol = will be used to represent the Fourier transformation ˜ operation. Whereas the symbol =−1 will represent the inverse h i −1 ˜ Fourier transformation. i. i.
246
. f (ω) = f (t) = 2π −∞ The above two relations form the convention used throughout this work.. =−1 . which is given by Z ∞ h i 1 −1 ˜ ˜ = (37.

247
247
(37.4)
.
Equations
• Vibrational degrees of freedom — linear: 3N − 5 — not linear: 3N − 6 • The so-called rigid rotor energy is Erot = J(J + 1)hBe . where Be ≡ is the rotational constant.3)
h 8π 2 I
(37. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. This section should not substitute for your studying of the rest of this material.Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. The equations are collected here simply for handy reference for you while working the problem sets.

f ¯ Z
∞
(37.5)
vib space
(37.
(37.• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib.8)
248
.7)
−∞
• The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω.6)
• The Fourier transformation is
˜ = [f (t)] = f (ω) =
f (t)eiωt dt.i ¯ vib. f (ω) = f (t) = 2π −∞
(37.

Part VII Kinetics and Gases
249
249
.

z) in coordinate (position) space. vyi . dzi .1. 250
250
. vz . y. t) which is in general a function of time. 2 2 • A sample of N molecules is characterized by its number density n∗ = • From the ideal gas law P V = nRT = N PL = RT = n∗ V
N RT L N . m is the molecular (or atomic) mass • Each particle of mass m has velocity v. The velocities of the particles are characterized by a probability distribution function for velocities F (vx .
38.38. hence a momentum of p = mv and a kinetic energy of KE = 1 mv · v = 1 mv 2 . vzi ). t. Physical Kinetics
We now turn our attention to the molecular level and in particular to molecular motion. This can represented in velocity space by dt dt dt dt the vector vi = (vxi . dyi . V
(L is Avogadro’s number):
Consider the ith particle at position xi = (x. vy . ¡ ¢ Its velocity is vi = dxi = dxi . kinetic theory of gases
A microscopic view of gases Consider a gas of point mass (m).

θ.The number of particles. t). (38. φ. NVv .. θ. (38. stationary distributions–those independent of time–are often encountered. n.b. F (v. θ. in velocity space is Z Z Z Z NVv = N F (v.2) Furthermore. φ. vz . t)dvx dvy dvz (38. then for many cases the velocity distribution will be isotropic–independent of θ and φ. θ. vy .1)
Vv Vv
It is more convenient to switch to spherical polar coordinates in velocity space (v. t) = F (v.3)
251
. F (v. Vv . φ). φ. v is simply a magnitude (not a vector)–it is the speed.
The probability distribution function then becomes F (v. t)dv = N F (vx . t) If we choose the origin of our coordinate system to be at the center of mass of the gas. t) = F (v. having velocities in a macroscopic volume. θ. φ).

For an ideal gas (V = P ).
38. This is the Maxwell’s distribution (of speeds). Molecular Collisions
The average speed of a particle can calculated from Maxwell’s distribution: Z ∞ Z ∞ m 3 − mv2 ) 2 e 2kT dv hvi = v = ¯ vF (v)dv = v 3 4π( (38. n RT |{z}
=L
A simple model for molecular collisions:
252
. So F (v) represents a distribution of speeds.We shall consider stationary isotropic distributions F (v).380658 × 10−23 is Boltzmann’s constant. It can be shown from ﬁrst principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38.2. n = = RT .4) 2πkb T where kb = 1.5) 2πkT 0 0 s r µ ¶ 8kT L Lk=R 8RT = = πm L Lm=M πM It will be convenient to deﬁne number density as n∗ ≡ N where N is the number V N P nRT LP ∗ of particles.

8)
Example: Ar at SATP (T = 298 K. Since the molecules are moving relative to one another we must ﬁnd the average relative velocity. v12 = h|v1 − v2 |i ¯ It can be shown that r v12 = ¯
√ √ collision 16RT = 2¯ =⇒ v = 2n∗ πσ 2 v .25 × 109 s−1 . frequency λ = 72. ∗ ∗ ∗ See Handout ∗ ∗∗ • The number of collisions equals the number of particles with their centers in V : number of collisions = n∗ πσ 2 v4t (38. P = 1 bar): v = 380.48 ¯ m . s
collision = 5.• Particles are hard spheres of radius σ. • A Particle moving at v sweeps out a cylinder of radius σ and length v4t =⇒ V = πσ2 v4t.5 nm
253
.6) • The collision frequency = n∗ πσ 2 v For the above model we need to ﬁnd the average collision frequency. ¯ πM frequency
(38.7)
From the above expression one deﬁnes the mean free path λ to be v ¯ / λ= √ 2n∗ πσ 2/ v ¯
LP n∗ = RT
=
RT √ 2P Lπσ 2
(38.

however.1. We can. We must account for the stoichiometry. Rate Laws
Consider a general four component reaction aA + bB = cC + dD (39.2) − dt dt dt dt BUT this is ambiguous because a moles of A reacts with b moles of B and a does not. That is. The Rate Laws of Chemical Kinetics
Thermodynamics described chemical systems in equilibrium. equal b. answer the question: How fast will the reaction occur?
39. For the study of chemical reactions it is important understand systems that can be very far from equilibrium.1)
The time dependence of this reaction can be observed by following the disappearance of either of the reactants or appearance of either of the products. from thermodynamics.
254
254
. For this we turn to the ﬁeld of chemical kinetics. in general. Will the reaction occur? We need kinetics. address the question.39. d[B] d[C] d[D] d[A] or − or or (39.

) (39. −b.We deﬁne the reaction velocity as v= 1 d[I] vi dt (39. B.6)
The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i . rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . rate laws are empirical.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration. but certainly not all. C.3)
where vi = −a. (39. v = f (conc. Many. or D. This deﬁnition is useful but must be used with caution since for complicated reactions all the v’s may not be equal. An example of this is ½ bB → cC + dD aA + (39. In general an overall reaction is made up of so called elementary reactions Reactant Reactant = → Product overall rxn (39.7)
Intermediates → Product
Note that we shall use an equal sign when talking about the overall reaction and arrows when talking about the elementary reactions Example
255
. c or d and I = A.5) For the most part.

at equilibrium vf = vb which implies kf [A]a [B]b = kr [C]c [D]d (39. Now.9)
where kf is the rate constant for the reaction to proceed in the forward direction and kr is the rate constant for the reaction to proceed in the reverse direction. (39. rate laws for overall reactions can not be determined by stoichiometry.Let 2A + 2B = C + D be the overall reaction. Trimolecular A + A + A → Product v = k[A]3 Trimolecular A + A + B → Product v = k[A]2 [B] Trimolecular A + B + C → Product v = k[A][B][C] Conversely.8)
The rate laws for elementary reactions can be determined from the stoichiometry molecularity elementary rxn rate law
Unimolecular A → Product v = k[A] Bimolecular A + A → Product v = k[A]2 Bimolecular A + B → Product v = k[A][B] . One possible set of elementary steps could be elementary rxn A + A → A0 A00 + 2B→ C + D A0 → A00 molecularity Bimolecular Unimolecular Trimolecular . Connection to thermodynamics Consider the overall or elementary reaction aA + bB cC + dD
kr kf
(39.10)
256
.

Next consider the reaction between molecular hydrogen and molecular bromine. H2 + I2 = 2HI. we have succeeded in connecting thermodynamics to kinetics BUT we have done so through the ratio of rate constants.bringing kr to the LHS and [A][B] to the RHS we get [C]c [D]d kf 0 = = Kc a [B]b kr [A]
0 where Kc is the thermodynamic equilibrium “constant. Objectives of chemical kinetics
257
. Moral: Kinetics is very much an empirical science. the reaction is not elementary. The velocity of a reaction is lost in this ratio and hence we still can not determine the speed of a reaction from thermodynamics.12)
The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 . This suggests that the reaction is elementary. v= k[H2 ][Br2 ]1/2 1+
k0 [HBr] [Br2 ]
(39. Moral: Kinetics is very much an empirical science. (39. Examples of rate laws Consider the (overall) reaction between molecular hydrogen and molecular iodine.
this does not obey any common form.13)
. H2 + Br2 = 2HBr.”
(39. In fact.11)
So. The observed rate law for this reaction is very complicated. The above two example are seemingly very similar but they have very diﬀerent observed rate laws.

2.• To establish empirical rate laws • To determine mechanisms of overall reactions • To empirically study elementary reactions • To establish theoretical links to statistical mechanics and quantum mechanics — This involve nonequilibrium thermodynamics–more diﬃcult • To study chemical reaction dynamics — the dynamics of molecular collisions that result in reactions
39. • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. Determination of Rate Laws
Concentrations c(t) are measured not rates. • Very fast (sec/subsec) reactions cause problems because the reaction goes faster than one can mix the reactants. To obtain the rate from the concentration we must take its time derivative dc(t) . Consequently no one experimental technique can be used. The rates of chemical reactions vary enormously from sub-seconds to years.
258
. • For medium reactions (min) either a continuous monitoring technique or a stopping technique can be used — A stopping technique used rapid cooling or destruction of the catalysts to stop a reaction at a given point. That is we must measure c(t) as a dt function of time and ﬁnd the rate of change of this concentration curve.

2.
259
. The main problem with such a method is that randomness in the concentration measurements gets ampliﬁed when taking the derivative.39.2. this gives the overall order of x + y • ﬂood with.2. 1. • initially v0 = kax by where a and b are the initial concentrations of A and B respectively • taking the log of both sides gives lnv0 = ln[kax by ] = ln k + x ln a + y ln b • a and b can be varied independently so both x and y can be determined. if there is an induction period 2. Integrated rate laws The above diﬀerential methods look directly at the rate law which is a diﬀerential equation. A so v ≈ kax [B]y 39.1. • problems 1. if the concentration drops very sharply 2. say. Method of initial velocities • for v = k[A]x [B]y rate laws. The diﬀerential equation is not solved. Diﬀerential methods based on the rate law Methods based directly on the rate law rely on the determination of the time derivative of the concentration. Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry.

type rate lawa) integrated rate lawa) 1st order 2nd order nth orderb)
1 vi 1 vi 1 vi 1 vi d[I] dt d[I] dt d[I] dt d[I] dt
= k[I] = k[I]2 = k[I]n
[I] = [I0 ]evi kt 1 = [I10 ] − vi kt [I]
1 [I]n−1
=
1 [I0 ]n−1
k[I] enyzme = km +[I] km ln [I0 ] + ([I0 ] − [I]) = −vi kt [I] a) [I] is the concentration of one of the reactants in an elementary reaction and vi is the stoichiometric factor for [I] (n. For example n = 3/2 is a three-halves order rate law. vi is a negative number).
− (n − 1)vi kt
260
..We now solve the diﬀerential equations to yield what are called the integrated rate law. The diﬀerential equations (rate law) and their solutions (integrated rate law) are simply listed here for a few rate laws. b) The order need not be an integer.b.

kr
(40.1) (40.40.5)
.1. Integration of the above yields ln k = ln A −
Ea Ea =⇒ k = Ae− RT RT
(40. take the log of this: ¸ kf = ln kf − ln kr . This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics
0 Kc =
kf ' Ka . d(1/T ) R where Ea is the Arrhenious activation energy. Temperature and Chemical Kinetics
40.3)
(A is the constant of integration). ln Ka = ln kr ∙ 261
261
(40.4)
Now.2)
(40. Temperature Eﬀects on Rate Constants
An empirical rate constant was proposed by Arrhenious: Ea d ln k = or dT RT 2 Ea d ln k = .

k = Ae− RT = aT j ej e−
Ea E 0 +jRT RT
= aT j ej e/ e RT = aT j e RT / −j
−E 0
−E 0
√
(40.10)
40.B) • Reaction rate determined by molecular collisions
262
. Theory of Reaction Rates
Simple collision theory (SCT) • Bimolecular reactions (A.9)
We can verify this by starting with the Arrhenious equation and substituting the above expressions.2.7)
(40.1. Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants.8)
(40. Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej
0
(40. Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT .Substituting the Arrhenious equation for the rate constants gives ¸ ∙ i h Ea Ear f − RT − ln Ar e− RT ln Ka = ln Af e ∙ ¸ Ear − Eaf Af = ln + Ar RT 40.6)
(40.1.

13)
[A][B]
= pπσ AB L
s
8RT − Em in e RT πLμ
(40.11)
is the reduced mass and σAB is the collision diameter.12)
• The rate constant for a bimolecular reaction is v k= [A][B] so SCT predicts k=
pzA B e− L
Em in RT
(40.
• The maximum reaction velocity is vmax = reaction velocity will be less because
zA B L
.14)
263
. but intuitively the actual
— the ability to react depends on orientation =⇒ a steric factor p — a minimum amount of collisional energy is required=⇒ e−Em in /RT • The actual reaction velocity is pzAB e− v= L
Em in RT
(40.— Collision frequency for A–B collisions s 8RT zAB = πσ AB L2 [A][B] πLμ where μ ≡
mA mB mA +mB
(40.

[A][B]
(40. • For the above example. thus we can apply thermodynamics to it. e.16)
Activated complex theory (ACT) • An intermediate active complex is formed during the reaction.18)
264
..17)
• The active complex is a state in the thermodynamic sense.g. A + B → (AB)‡ → products. ACT is not limited to bimolecular reactions.• Comparison to the (temperature corrected) Arrhenious equation suggests s 8RT 1 e2 (40. (40.15) A = pπσ AB L πLμ and 1 Ea = Emin + RT 2 (40. the equilibrium constant is deﬁned as
‡ Ka =
a‡ low [‡] ' aA aB conc.

it can be shown that f = kb T /h where kb is Boltzmann’s constant and h is Planck’s constant. in what is called a reaction network. there is many steps from initial reactants to ﬁnal products. — From statistical mechanics. Multistep Reactions
Up to now. f — accounts for the fraction of activated complex that becomes product.22)
40.3. Reactions may occur in series or in parallel or both. In general.20)
which can be written as
‡ Ka = e−
4G‡ RT
= e−
4H ‡ RT
e
4S ‡ R
(40.21)
where 4G‡ = 4H ‡ − T 4S ‡ . the reactions we have studied have been single step reactions. h
(40.19)
• Thermodynamics tells us that
‡ 4G‡ = −RT ln Ka
(40. • The ACT reaction rate constant now becomes k= This is Eyring’s equation kb T − 4H ‡ 4S‡ e RT e R .• Deﬁnition: transmission factor. Parallel reactions:
265
. • The reaction rate constant for reactants going to products for ACT is
‡ k = f Ka =
kb T ‡ K h a
(40.

They are of the form k1 k2 A→B→C (40. dt
which. for example. B and C are determined by the system of diﬀerential equations: − d[A] = k1 [A] dt d[B] = k1 [A] − k2 [B] dt d[C] = k2 [B].
1 A + B1 → C
k
(40. when solved yields [A] = [A0 ]e−k1 t ¢ k1 [A0 ] ¡ −k1 t [B] = − ek2 t e k2 − k1
¶ µ k2 e−k1 t − k1 ek2 t [C] = [A0 ] − [A] − [B] = [A0 ] 1 − k2 − k1
• See in class animation
266
.23)
A + B2 → D • The rate constant for the disappearance of [A] is simply the sum of the two rate constants: k = k1 + k2
k2
Series reactions: • Series reactions necessarily include and intermediate product.• Parallel reactions are of the form.24) • The concentrations of A.

4.40. Initiation: Typically a molecule M reacts to form some highly reactive radical M → R·.
267
. The simplest chain reactions have three distinct steps (discussed below) Chain reactions are extremely important in polymer chemistry Steps of a chain reaction 1. Chain Reactions
Chain reactions are reactions which have at least one step that is repeated indefinitely.

2. This step repeats an indeﬁnite number of times. 3. Termination: The radicals interact with each other or with the walls of the container to forma stable molecule R0 ·+R0 · → M000 or R0 ·+wall → removed
268
. R·+M0 → M00 + R0 ·. Propagation: The radical formed in the initiation step reacts with some so molecule M0 to form another molecule M00 and another radical R0 ·.

2)
• The van der Waals gas equation of state P = or
n2 a nRT − 2 V − nb V
(41. a particular particle has much less signiﬁcant interactions with the other particles. nRT
m V
(41. Gases and the Virial Series
Unlike liquids and solids. Equations of State
Recall from last semester several of the equations of states for gases.1)
(41. • The ideal gas equation of state P V = nRT. We will now look in detail at the gases. The equation of state can also be expressed in term of density ρ = ρ= mP .3)
a RT − 2.41.
41.4) Vm − b Vm where the parameter a accounts for the attractive forces among the particles and parameter b accounts for the repulsive forces among the particles P = 269
269
.1. This simpliﬁes the theoretical treatment of gases. (41.

9)
B(T ).
• z can be expended in a power series called the virial series.2. are called the virial coeﬃcients. Conceptually B(T ) represents pair-wise interaction of the particles.7)
41. etc. C(T ). The Virial Series
Deﬁnition: Compressibility Factor: z =
PV nRT
=
P Vm .
n • For a real gas z must approach unity upon dilution ( V → 0). + ··· . (41.8)
³n´
1 z = 1 + B(T ) Vm
¶
1 + C(T ) Vm
1 + D(T ) Vm
(41.
270
. etc. C(T ) represents triplet interactions.6)
• Redlich-Kwang P = (41.• Berthelot • Dieterici
P =
nRT n2 a a RT − − = 2 2 V − nb T V Vm − b T Vm
an a
(41. The virial series in powers of z = 1 + B(T ) or µ V
n V
is + C(T ) µ ³ n ´2 V ¶2 + D(T ) µ ³ n ´3 V ¶3 +··· . RT
• z is unity for an ideal gas because for such a gas P V = nRT.5)
RT e− RT Vm nRT e− RT V = P = V − nb Vm − b nRT n2 a a RT −√ −√ = V − nb Vm − b T V (V − nb) T Vm (Vm − b)
(41.

41. 1−x Therefore b a +1+ + z=− RT Vm Vm the ﬁrst term is proportional to in the series expansion. RT Vm Vm
(41. D(T ) = b3 .10)
to get
V / a /T Vm R / P Vm = − m / 2 RT R / Vm − b RT Vm /T a Vm − = Vm − b RT Vm 1 a = − b RT Vm 1 − Vm but
P Vm RT
(41. C(t) = b2 .
(41.12)
The ﬁrst term is of the form
1 1−x
1 = 1 + x + x2 + · · · . etc.11)
= z so z= 1 a − .15)
This series can now be compared term by term to the virial series to give expression for the virial coeﬃcients: ³ a ´ .14)
1 Vm
and so it can be combined with the
term
µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· .13) (41.16) B(T ) = b − RT
271
.1. hence
1 Vm
µ
b Vm
¶2
+ ··· . b RT Vm 1 − Vm which has the power series expansion (41. (41. Relation to the van der Waals Equation of State Recall the van der Waals equation P = multiply both sides by
Vm RT
a RT − 2 Vm − b Vm
(41.2.

3. The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature. One ﬁnds (see m homework) B(T ) B 0 (T ) = .2. (41. 41.18)
The relation of this expansion to the one in V1 can be obtained.41.2. (41.17) = 1 + C(T ) Vm Vm ³ ´2 . The gas behaves more like an ideal The lowest order correction are now V1 m gas at Tb then for other temperatures. Tb .2. The virial series at Tb becomes µ ¶2 µ ¶ µ ¶3 1 1 1 z(T = Tb ) = 1 + 0 + C(T ) + D(T ) + ··· Vm Vm Vm µ ¶3 µ ¶2 1 1 + D(T ) + ··· . The Virial Series in Pressure One can also expand the compressibility factor in pressure z = 1 + B 0 (T )P + C 0 (T )P 2 + D0 (T )P 3 + · · · . (41.19) RT
272
.

• Estimates based on Beattie-Bridgeman constants: c A0 − 3.23) (41.4. (41. for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 .25) 128Pc T (41.C 0 (T ) = and D0 (T ) =
C(T ) − B(T )2 (RT )2
(41. C(T ) = RT T B0 bc D(T ) = . b.21)
41. RT T A0 a B0 c − B0 b − 3 .22) (41.20)
D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3
(41. Estimation of Virial Coeﬃcients The virial coeﬃcients can be estimated using empirical equations and tabulated parameters.24)
273
. a. c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly. B0 . T3 B(T ) = B0 − where A0 .2.

• Positive α means the volume of the ﬂuid increases with increasing temperature. the compressibility factor. V and T behavior of dense ﬂuids (e. P ) = ∂T P ∂P T We can change this from a extensive property equation to an intensive property equation by dividing by V : µ ¶ µ ¶ 1 ∂V 1 ∂V dV = dT + dP. V and T behavior
We shall brieﬂy consider the P.1) dV (T. we consider the total derivative ¶ ¶ µ µ ∂V ∂V dT + dP. Taking volume as a function of P and T. • κT is diﬀerent from z. • Positive κT means the volume of the ﬂuid decreases with increasing pressure. Behavior of Gases
42. 274
274
. κT describes the change in volume with pressure. α describes the change in volume with temperature. P.g.1. liquids).
κT is the isothermal compressibility • At a given temperature. (42.42..
• At a given pressure. V V ∂T P V ∂P T | {z } | {z }
α −κT
α is the coeﬃcient of thermal expansion.

3)
In general. P Ã ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42. At constant T ¶ ¶2 µ ∂V ∂V (P − P0 ) + (P − P0 )2 + · · · V (P ) = V0 + ∂P ∂P T | {z T } µ
−V0 κT
(42.1.
275
. it is. P0 . the compressibility and expansion of liquids (and solids) are very small.2. So one can expand the volume in a Taylor series about a known pressure.
V (P ) ≈ V0 [1 − κT (P − P0 )] . absurd to treat a liquid as an ideal gas).1.
(42. Starting with the ideal gas law: V = nRT .5)
This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so). α and κT for liquids and solids
Ã ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P
=n R / /T
(42.42.. of course.4)
so. α and κT for an ideal gas As an exercise we shall calculate α and κT using the ideal gas equation of state (n.1.2) = = V ∂P T V ∂P V P
T
=
and
n/T 1 /R/ 1 1 nRT = = (P V ) P P /R/ P n/T | {z }
=nRT
1 α= V
µ
∂V ∂T
¶
P
1 = V
42.b.

11)
P
276
.8) κT − ∂P T rule ∂T V
42. The Relationship Between CP and CV To ﬁnd how CP and CV are related we begin with ¶ µ ∂H .7)
As one ﬁnal point.
(42. Heat Capacity of Gases Revisited
This section is a review from the ﬁrst semester with an additional example beyond the ideal gas. we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42.2.9)
¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42.2.
V (T ) ≈ V0 [1 + α(T − T0 )] .10) CP = ∂T ∂T P ∂T P P ¡ ¢ ¡ ¢ note ∂U P is not CV we need ∂U V . Use an identity of partial derivatives ∂T ∂T µ ∂U ∂T ¶ =
P
µ
∂U ∂T
¶
+
V
µ
∂U ∂V
¶ µ
T
∂V ∂T
¶
(42.Likewise at constant P ¶ ¶2 µ ∂V ∂V (T − T0 ) + (T − T0 )2 + · · · V (T ) = V0 + ∂T P ∂T T | {z } µ
V0 α
(42.H = U + PV CP = ∂T P so µ
(42. 42.6)
so.1.

Explicit in P : Replace µ 2. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P
∂V
P
¡ ∂P ¢
(42. Then ∂T µ ∂U ∂T µ CP = CV + Finally CP = CV + T µ ∂V ∂T ¶ ∙ µ ¶ ¸ ∂P T −P +P / / ∂T V P µ ∂V ∂T ¶ µ
P
¶
(42. ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P .14)
V
For solids and liquids: µ so ∂V ∂T ¶ = V α.16) κT For gases we need the equation of state which often is conveniently explicit in P or V but not both CP = CV + 1.13)
∂P ∂T
¶
(42.15)
P
V
α2 T V (42.18)
277
.thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42.17)
T
V
∂T with − ¡ ∂V ¢P ∂P T
¡ ∂V ¢
(42. µ ∂P ∂T ¶ = α κT (42.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P .

One term viral equation (equation of state: V = nRT + nB). nRT − P2 / RT n
(42. Ideal gas (equation of state: P V = nRT ): This equation is easily made explicit in either P or V so we don’t need any of the above replacements ¶ µ ¶ µ ∂P ∂V (42.20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 . This is explicit P in V so use case 2 above ¶ µ ¶ ¶ ¡ ∂V ¢ µ µ ∂P ∂V ∂V ∂T ¡ ∂V ¢P CP = CV + T = CV − T (42. = ∂T P P
∂T − ¡ ∂V ¢P = − ∂P T
µ
∂V ∂P
¶
T
=−
nRT .19) CP = CV + T ∂T P ∂T V nRT nR nR = = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R 2.Examples 1.24)
278
.22)
Thus CP
! ¶Ã nR P (R + P B 0 ) + nB 0 = CV + / T P RT / ¶2 µ P B0 = CV + nR 1 + R µ CP m ¶2 µ P B0 = CV m + R 1 + R
(42. P2
(42.23)
or
(42.21)
so
¡ ∂V ¢
nR P
+ nB 0 / P (R + P B 0 ) n = .

V ) = U(T ) (independent of V ).27)
Also recall that −wrev is the maximum possible work that can be done in an expansion.
Isothermal expansion • For the case of a ideal gas.25)
V1
As we learned last semester the value of w depends on Pex during the expansion.
279
.42. Expansion of Gases
Expanding gases do work: −w = Z
V2
Pex dV
(42. 42. −wrev = −wmax . So. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1. −wrev = For an ideal gas (P =
nRT ) V
Z
V2
Pgas dV
(42. U (T. Isothermal expansion T is constant 2.3. Namely Pgas = Pex .3.26)
V1
this becomes Z
V2
−wrev =
V1
µ ¶ V2 nRT dV = nRT ln V V1
(42. So for isothermal expansion 4U = 0 = q + w =⇒ q = −w. Recall that if the expansion is reversible.1. there is always an intermediate equilibrium throughout the expansion. Adiabatic expansion q = 0.

V2 ): CV dT = Z
T2
(42.29)
(42.31)
If CV (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ V2 T2 ¯ = −nR ln (42. V1 ) to (T2 . Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 . V2 ). Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 . V
(42.32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) . in terms of molar heat capacity
2
T2 ¯ CV m ln T1
µ
¶
V2 = −R ln V1
µ
¶
(42. Or.33)
280
. V1 ) to (T2 . • For an ideal gas dU = −P dV = −nRT dV V (42.28)
42. dU = dw = −Pex dV = −P dV (reversible).3.Adiabatic expansion • Since q = 0.30)
T1
CV dT = T
Z
V2
V1
−nR dV.2.

37)
If CP (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ P2 T2 ¯ = nR ln (42. CP = µ ∂H ∂T ¶
(42.40)
281
.34)
=⇒ dH = Cp dT = V dP
(42.3. P
(42. change)
/ / dH = dq + dw + P dV + V dP
dH = V dP. Now. Or.36)
CP dT = T
P2
P1
nR dP.39)
From the above two cases µ ¶ µ ¶ µ ¶ R −R P2 V2 T2 = ¯ ln = ¯ ln ln T1 P1 V1 CP m CV m
(42.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) . dH = dU + P dV + V dP (because both P and V can. in terms of molar heat capacity
2
T2 ¯ CP m ln T1
µ
¶
P2 = R ln P1
µ
¶
(42. P2 ): Z T2
T1
nRT dP P Z
(42.42. When P is the more convenient variable What if P is the more convenient variable? Then use H instead of U Let us still consider an adiabatic expansion H = U + P V. P1 ) to (T2 .35)
P
For an ideal gas this becomes
Cp dT = Going from (T1 . in general.3.

(42. Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0).
282
. In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).41)
¶
V1 = γ ln V2
µ
¶
V1 = ln V2
µ
¶γ
(42.3.43)
42.42)
but Pi Viγ are arbitrary so this implies P V γ = constant (** NOTE: The axes should be reversed **)
¶γ
⇒ P2 V2γ = P1 V1γ .So
P2 ln P1 µ ¶ µ
µ
¶
hence
P2 ln P1
V2 = −γ ln V1 P2 P1 ¶ = µ V1 V2
Thus
µ
µ ¶ ¯ V2 CP m = − ¯ ln V1 CV | {zm }
≡γ
(42.4.

3. for Joule type expansion the temperature of the gas does not change. Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the ﬁgure below
¡ ∂U ¢
283
.This implies 4U = q + w = 0.44)
U
. We want to ﬁnd Identity: ¡ ∂T ¢
∂V
(42. ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z }
1/CV
µ
∂T ∂V
¶
(42. Internal energy is constant.5. 42. For real gases this is not strictly equal to zero. Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0.45)
U
For an ideal gas ∂V T = 0 (since U(T. V ) = U(T )). That is.

48)
(42.46)
(42. 4U = U2 − U1 = wL + wR = P1 V1 − P2 V2 Thus U2 + P2 V2 = U1 + P1 V1 ⇒ H2 = H1 For Joule-Thomson expansion the enthalpy is constant.50)
H
284
.47)
(42. Now. We want to ﬁnd Identity: µ ¡ ∂T ¢
∂V
(42.The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 .49)
H
≡ μ. ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z }
1/CP
∂T ∂P
¶
(42. The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 . (the Joule-Thomson coeﬃcient).

μ = CP m Limts: • Low T : B 0 is positive and B is negative. so μ is negative–the gas warms upon expansion • The Joule-Thomson inversion temperature is the temperature where μ = 0.Recall the useful identity µ Thus ∂H ∂P ¶ =V −T µ ∂V ∂T ¶ (42.52)
Example: The one term virial equation: (equation of state P V = nRT + nB) µ ¶ nRT 1 −nRT 0 − nB + + nT B μ = CP P P −B + T B 0 .51)
T
P
¡ ¢ −V + T ∂V P ∂T μ= CP
(42. so μ is positive–the gas cools upon expansion • High T : B 0 is nearly zero and B is positive.53)
285
. (42.

1. (43. but also dH = T dS.2) dS = T T T1
dq=C dT
Isothermal expansion of an ideal gas (P V = nRT ): • Recall that for isothermal expansion of an ideal gas dU = 0 = T dS − P dV dV ⇒ dS = P T . This is not a problem though since entropy is a state function.1)
At constant P : (use H = U + P V instead of U)
P — dH = dU +P dV +V dP = dq−P dV +P dV +V dP .43. dS = T T T1
(43. So dH = dq =⇒ dq=T dS dH = CP dT. 286
286
. Entropy change for changes in temperature. Entropy of Gases
43. • At constant V : — dU = dq + dw
dq=CV dT
=⇒
dU = CV dT. Calculation of Entropy
Entropy must be calculated along reversible paths. So Z T2 CV CV dT =⇒ 4S = dT. So Z T2 CP CP dT =⇒ 4S = dT. but also dU = T dS.

4)
If two variables change in going from the initial to ﬁnal states break the path into two paths in which only one variable changes at a time.3)
• Using the equation of state to express V1 and V2 in terms of P1 and P2 .6) VA + VB . V1 P1 /R / n / T
P1
/R / n / T
(43. V V1
(43. there are simply two separate equations: 4SA = nA R ln and 4Smix = 4SA + 4SB (43. VA 4SB = nB R ln VB + VA VB (43.• Using the equation of state nRdV =⇒ 4S = dS = V
Z
V2
V1
V2 nR dV = nR ln .5)
287
. Entropy of Mixing of an ideal gas
• Since the gas is ideal. V2 P2 dS = nR ln = nR ln P2 = −nR ln .

P2 → P θ as S θ . V =
Hence
¶
T
∂V =− ∂T
µ
¶
P
=−
nR − nB 0 P
(43. Entropy of Real Gases Consider the question: How does S → S ideal as P → 0 ? Use Maxwell relation nRT + nB.7)
43.11)
Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar). P So ¡ ∂S ¢ µ ∂S ∂P
∂P T
= −
¡ ∂V ¢
∂T
P
and single term viral equation.13)
288
.8)
µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1
(43. so
ideal ideal S2 − S1 = −nR ln
(43. ⎛ ⎞
1/XA 1/XB
⎜ nA + nB nB + nA ⎟ ⎜ ⎟ + nB ln 4Smix = R ⎜nA ln ⎟ = −R (nA ln XA + nB ln XB ) nA nB ⎠ ⎝ | {z } | {z } (43. So. So.12)
ideal Deﬁning S2 .10)
Thus
ideal ideal S2 − S1 = S2 − S1 − nB 0 (P2 − P1 )
(43.1.9)
For an ideal gas B 0 = 0.
S(P θ ) = S θ − nB 0 P θ
(43.• Recall Avogadro’s principle: n ∝ V for an ideal gas. this becomes S2 − / 1 S
ideal ideal = S2 − / 1 S ideal
− nB 0 (P2 − P1 )
(43.1.

The entropy at any P and T can be obtained expresses as S(T.14)
(43. P ) = S θ (T ) − nR ln P − nB 0 P Pθ (43. P ) − nB 0 P Thus S(T.15)
289
. P ) = S ideal (T.

Equations
• The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T
¶3 2
e 2kb T v2 . This section should not substitute for your studying of the rest of this material.18)
290
290
.
−mv2
(43. The equations are collected here simply for handy reference for you while working the problem sets. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations.Key Equations for Exam 3
Listed here are some of the key equations for Exam 3.17)
RT λ= √ 2P Lπσ 2
(43.16)
• The average speed of a particle is hvi = • The mean free path is
r
8RT πM
(43.

19)
• The relation between the rate constant and the thermodynamic equilibrium constant is kf Kc = (43.20) kr • The Arrhenious equation k = Ae− RT
Ea
(43.24)
z=
(43.22)
• The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2.25)
• The virial series is µ ¶ µ ¶2 µ ¶3 1 1 1 z = 1 + B(T ) + C(T ) + D(T ) + ··· . Vm Vm Vm • Relation between heat capacities for an ideal gas: CP m = CV m + R
(43. Vm − b Vm P Vm PV = .21)
• Important thermodynamic relation: 4G = 4H − T 4S • Eyring’s equation is k= kb T − 4H ‡ 4S‡ kb T − 4G‡ e RT = e RT e R h h (43.23) (43.27)
291
.26)
(43. nRT RT (43.• The reaction velocity is v=
1 d[I] vi dt
(43.

Part VIII More Thermodyanmics
292
292
.

Law of rectilinear diameters: The average density [ρave = 1 (ρliq + ρvap )] is 2 linear in temperature.44. It is characterized by a critical temperature. Critical Behavior of ﬂuids
The point on the top of the coexistence curve is called the critical point. Tc . Critical Phenomena
44.1. and a critical density ρc .
293
293
.

Gas Laws in the Critical Region
The vapor pressure of a substance is taken from the gas laws as the pressures where A1 = A2 in the above ﬁgure.44.1.1.
294
. Simple gas laws do not work well near critical points.

6)
These values can be used to ﬁnd the compressibility factor. z.2. Tc . setting 2 m the ﬁrst and second derivatives at the critical point equal to zero we get ¯ dP ¯ ¯ = −RTc + 2a = 0 (44.2) 3 dVm ¯c (Vmc − b)2 Vmc
and
solving these three equations for Pc . 8a .375 3/8 = 0.4) (44.1.33
295
.375 2/e2 ' 0. Vmc ) Pc = a RTc − 2 .27 0. Tc and Vmc gives Vmc = 3b. dVP = 0) at the critical point.3)
(44. That is (for the van der Waals Equation) zc = 0. RTc 8 (44.375 for all gases.375.44. Vmc − b Vmc
2
(44.7)
Notice that both a and b whose values depend on the particular gas have dropped out. Tc = 27bR a . at the critical point zc = Pc Vmc 3 = = 0. Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc . The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0.1)
dP d There is an inﬂection point ( dVm = 0. Pc = 27b2
¯ d2 P ¯ ¯ = 2RTc − 6a = 0 2¯ 4 dVm c (Vmc − b)3 Vmc
(44.5) (44. So.

dn. One can deﬁne unitless “reduced” variables Tr = T /Tc .3. and Vr = V /Vc . 1. Suppose some amount of material. β denote liquid (or solid) and vapor phases.V = −P
For a spontaneous process A deceases (dA < 0)
z }| { (dVα + dVβ )
¡ ¢ + μβ − μα dn
At equilibrium dA = 0. the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T.
296
. ∗ ∗ See Fig. This is actually not too far from the truth experimentally. goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn
= 0 since V is constant
• (dA)T. Then zr = Pr Vrr . then for a given T .18 Laidler&Meiser ∗ ∗
44. Phase Equilibrium
Consider a homogeneous substance consisting of two phases α and β at a constant T and V.44. The Law of Corresponding States
We have found that zc is predicted by the equations of state to be independent of the particular gas.2. Pr = P/Pc . When α. This implies μβ = μα is the condition for equilibrium. RT zr is a “universal” function–it is nearly the same for all gasses.

= Vm . µ ∂S ∂n ¶ µ ¶ (44.n
P. ∂G S=− ∂T So.8)
(44. So again μβ = μα is the condition for equilibrium.12)
T
Now the total diﬀerential of μ is
m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T.10)
But S = nSm (T.P = μβ − μα dn. P ) = ∂T P ∂P T dμ(T.13)
297
.1.11)
P
Similarly.3. dG = −SdT + V dP + μdn Now.
(44. 44. ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm . The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances.T
µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− .¡ ¢ For phase changes at constant T and P then (dG)T.
(44. P ) = −Sm dT + Vm dP
−S
V
(44. P ) so.9)
P.
µ
∂μ ∂P
¶
(44.

14)
=
This is the Clapeyron Equation
4φ Hm T 4φ Vm
(44.17)
Substituting this into the Clapeyron equation gives 4v Hm 4v Hm P dP = = RT dT RT 2 T P 4v Hm dT dP = P R T2 Now we identify
dP P
(44.18) (44.19)
Collecting the T ’s on one side of the equation and the P ’s on the other we get (44.3. Now 4v V = Vm. 4v V = RT P (44. −Smα dT + Vmα dP = −Smβ dT + Vmβ dP Now Smα − Smβ −4φ Sm dP = = dT Vmα − Vmβ −4φ Vm 4φ Hm dP = dT T 4φ Vm
4S= 4H T
(44.20)
= d(ln P ) and
dT T2
= −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.liq ' Vm. The Clapeyron Equation At equilibrium μβ = μα so.16)
44.2.3.3. consider the liquidvapor phase transition.21)
d(ln P ) = −
298
.15)
(44.vap − Vm. Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition.44.vap Assuming the vapor phase obeys the ideal gas equation of state.

“A diamond is not forever!” At equilibrium μα = μβ this implies (for incompressible liquids and solids) μª + Vmα (P − P ª ) = μª + Vmβ (P − P ª ) α β (44.Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation.22)
44.24) α β
299
. most other common liquids • Solid—solid — rhombic sulfur—monoclinic sulfur — grey tin—white tin — graphite—diamond
For example a diamond at STP is metastable with respect to graphite.23)
This can be rearranged so that terms independent of pressure (the standard chemical potentials) are one side and the terms that depend of pressure are on the other side μª − μª = (Vmβ − Vmα ) (P − P ª ) (44. (44. Equilibria of condensed phases
Examples • Solid—liquid — ice—water.4.

25)
We make the good approximation that 4f Hm is independent of T and solve the Clapeyron equation Z → 4f Vm dP Tf 4f Vm (P − P ª ) dT = ⇒ ln ª = (44.
44.Thus for any given T only one P allows for equilibrium.26) 4f Hm 4f Hm Tf → T
ª where Tf is the freezing temperature at standard pressure (1 bar). Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44.27)
300
.5. At temperatures above the critical point there is no distinction between vapor and liquid. T for a system which shows the lines of equal chemical potential • Critical Point: The terminal point of the liquid-vapor line. • Triple Point: The point where all three phases coexist in equilibrium: μsolid = μliq = μvap (44. Triple Point and Phase Diagrams
Deﬁnitions • Phase Diagram: A graph of P vs.

Transport Properties of Fluids
Transport properties of matter deal with the ﬂow (or ﬂux) of some property along a gradient of some other property.1)
301
301
. of material from high concentration to low concentration so as to establish an equilibrium. Flux: movement of something through a unit area. Viscosity: The ﬂux of momentum down a velocity gradient 3. J= 1 dn A dt (45. Diﬀusion: The ﬂux of material down a concentration gradient 2.45. Diﬀusion
At equilibrium concentration on a bulk solution will be uniform. J. So if there exists a concentration gradient there will be a net ﬂux. We now consider three transport properties of ﬂuids: 1.1. Thermal Conductivity: The ﬂux of energy down a temperature gradient
∗ ∗ See Transport Phenomena handout ∗ ∗
45.

∂t ∂x (45. The change in concentration in a lamina between x and dx with time is given by the ﬂux in minus the ﬂux out of the lamina: J(x) − J(x + dx) ∂J ∂C = =− ∂t dx ∂x Using Fick’s ﬁrst law for J ∂ ∂C ∂C = D .2)
(45.5)
302
.The ﬂux of material through a plane depends on the concentration diﬀerence J = −D dC 1 dn dC =⇒ = −D dx A dt dx
where D is the diﬀusion constant dC 1 dn = −D A dt dx This is Fick’s ﬁrst law of diﬀusion (in one dimension).3) (45. ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diﬀusion: ∂ 2C ∂C =D 2.4) (45.

6)
2. i. The solution for two special boundary conditions are of interest and will simply be presented here without derivation 1.e.7)
where erf and erfc are tabulated functions respectively called the error function and complementary error function. The tendency of a liquid to ﬂow at the same velocity throughout. η. t) = √ e− 4Dt 2 πDt
(45. t) = C0 2 π 0 ¶¸ ∙ µ x 1 C0 1 − erf √ = 2 4Dt ¶ µ 1 x = C0 erfc √ 2 4Dt " (45.. Numerous methods of solution exist for this equation but they are beyond the scope of the course. Step function solution # Z √x 4Dt 1 1 2 −√ e−y dy C(x. Point source solution
x2 C0 C(x. is the resistance to diﬀerential ﬂuid ﬂow.
303
.2. Viscosity
Viscosity.The solution of this partial diﬀerential equation depends on the boundary conditions.
45.

lenght·time
1 poise
Poiseuille’s Formula • Applies to Laminar (nonturbulent) ﬂow • For a liquid ﬂowing trough a tube (radius r. the diﬀerence in pressure on either side of the tube. i. length l).dv The frictional (viscous) force is F = ηA dx .8) 4t 8ηl where 4P is the driving pressure..)
mass .9)
Stoke’s law: spheres falling through ﬂuids
304
. the volume of ﬂow 4V in time 4t is πr4 4P 4V =− (45. (The units of η are g = cm·s . • For a gas 4V πr2 = 4t 16ηl µ
2 Pi2 − Pf P0
where Pi is the inlet pressure.
¶
(45.e. Pf is the outlet pressure and P0 is the pressure at which the volume is read.

11)
• Related to diﬀusion constant:
=
kT 6πηr
(45.• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv. Consider a slab of solid material of area A between two large parallel plates a distance D apart.8 m/s2 ). Stewart and E. Thermal conductivity
(This section closely follows parts of chapter 8 in Transport Phenomena by R.B. W.E. Bird. The plates are held at constant but diﬀerent temperatures T1 and T2 (T1 > T2 ) for a suﬃciently long time that a steady state exists.
305
. κ. 3
where g is the
• Terminal velocity is reached when Ff + Fg = 0 giving −f vterm + vterm = using f = 6πηr vterm 4π r/ (ρ − ρ0 )g / 3 2r2 (ρ − ρ0 )g ¡ ¢ = = 9η 3 6π ηr / / D= kT f
f =6πηr
4πr3 (ρ − ρ0 )g = 0 3 4πr3 (ρ − ρ0 )g 3f
(45.10)
(45. Lightfoot Wiley New York 1960) The thermal conductivity. Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9. of a material is a measure of the tendency of energy in the form of heat to ﬂow through the material.3.12)
45.
4πr3 (ρ − ρ0 )g. N.

Under such conditions. whereas the thermal conductivity of most liquids decrease with increasing temperature. Thermal conductivities are positive quantities so Fourier’s law says that heat ﬂow down a temperature gradient. Thermal Conductivity of Gases and Liquids ∗ ∗ See Reduced thermal conductivity handout ∗ ∗ From this handout we see that typically the thermal conductivity of gases at low densities increases with increasing temperature. from hot to cold. a linear steady state temperature distribution across the material is established.13) A dt D If we take the limit where D becomes inﬁnitesimally small (D → dx) we obtain a diﬀerential form of this equation: 1 dq dT = Qf = −κ . (45. This is called Fourier’s law of heat conduction (one-dimensional version). i.14) A dt dx where Qf is the heat ﬂux. (45.1..3. 45.
306
. And a constant rate of heat ﬂow dq is needed to maintain dt the temperature diﬀerence 4T = (T1 − T2 ) 4T 1 dq = −κ .e.

3.2. There is no analog to superconductivity for thermal conductivity. the thermal conductivity of solids have to be determined experimentally because many factors contributing to the thermal conductivity are diﬃcult to predict. In general metals are better heat conductors than nonmetals and crystals are better heat conductors than amorphous materials. The Wiedemann.15)
307
.45. The Lorenz number is taken as constant because it is only a very weak function of temperature with a change of 10 to 20% per 1000 degrees being typical. Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ). Dry porous materials are poor heat conductors Rule of Thumb: Thermal conductivity and electrical conductivity go hand in hand. (45. Thermal Conductivity of Solids For the most part. The Wiedemann. Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. κel for pure metals: κ = L = const.

4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity. M1 X1
where M1 is the molecular weight of species 1
n2 L solution
46. For example.2)
.46.2. Solutions
Solutions are mixtures of two or more pure substances. So. n1 +n2
• mole fraction X2 = • molality m = • Molarity c2 =
X1 = 1 − X2
1000X2 .1. say. one also needs to keep track of the amount of individual species in solution
46. volume. Partial Molar Quantities
Thermodynamic properties. 308
308
(46.1)
(46. Measures of Composition
There are several measures of composition of solutions • mole ratio r =
n1 n2 n2 . in addition to the parameters needed to characterize a pure substance. in general change upon mixing X 4mix = properties of soln − properties of pure.

n1 (46. P.1. Notation The study of solutions brings with it here for future reference. ∂ni
T.n2 ∂n2 T.P.2. Material Pure liquid i Vi• • Pure liquid i per mole Vmi Whole solution V Solution/(total moles) Vm ¯ Partial molar of i in solution Vi Apparent molar (of solute) φ V Reference state Viª a large number of symbols which we collect
Hi• • Hmi H Hm ¯ Hi φ H Hiª
Si• • Smi S Sm ¯ Si Siª
G• i • μi G Gm μi μª i
309
. n1 .In general.n1 .nj
So now for the more general case of mixtures the chemical potential of a species of the partial molar free energy for that species.P.n1 (46.n2 ∂P T. rather than simply the molar free energy as it was earlier.n1 . ∂ni
T.P.n2 ∂n1 T. dG = ∂T P.n2 ∂n2 T. n2 ). 46. the partial molar volume.P.nj
Similarly ¶ ¶ ¶ ¶ µ µ µ µ ∂G ∂G ∂G ∂G dT + dP + dn1 + dn2 .P. n1 and n2 : V (T.n2 ∂P T. So.n1 .n1 . P.4) ³ ´ ∂G ≡ μi .3) ³ ´ ∂V ¯ ≡ Vi . the total derivative is ¶ ¶ µ ¶ ¶ µ µ µ ∂V ∂V ∂V ∂V dV = dT + dP + dn1 + dn2 . it is a function of T.n2 ∂n1 T. ∂T P.P.

dn2 = n2 dλ. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46. so change each amount of substance proportional to the amount substance present.
310
.8)
4mix V can be positive.6)
That is. The total volume. one unit of baseballs are mixed with one unit of books.5) ¯ Now.46. 4mix V < 0. the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. So. 2. For example.2.7)
(46. Vi depends on concentration. (46. is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state. negative or zero. dn1 = n1 dλ.2.
1. however. 4mix V > 0. More speciﬁcally 4mix V
• • = V − (Vm1 n1 + Vm2 n2 ) ¡ ¢ • • ¯ ¯ = V1 n1 + V2 n2 − (Vm1 n1 + Vm2 n2 ) ¡ ¡ ¢ ¢ • • ¯ ¯ = V1 − Vm1 n1 + V2 − Vm2 n2
¢ ¡ dλ ¯ ¯ ¯ ¯ dV = V1 n1 + V2 n2 dλ =⇒ V = V1 n1 + V2 n2
(46. one unit of baseballs are mixed with one unit of basketballs.

Activity (a brief review)
Henry’s law limit
Recall that activity gives a measure of the deviation of the real state from some reference state
311
. the ideal state for Raoult’s law 2. all neighboring molecules are same as the given molecule 2. all neighboring molecules are diﬀerent than the given molecule 2.3.1. inﬁnite dilution limit 1. neat (pure) solvent limit 1.3. the ideal state for Henry’s law
Raoult’s law limit 46.46. Reference states for liquids
For liquids there are two more convenient ideal states 1.

g.3. pressure. and ζ ª is the value of ζ at the reference state.). γi ≡ which we can rearrange as ai = γ i g(ζ).2.9) ζ→ζ ª g(ζ) where g(ζ) is any reference function (e.. mole fraction. This implicit deﬁnition is awkward so for convenience one deﬁnes the activity coeﬃcient as the argument of the above limit. concentration etc.11) The deﬁnition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) That is γ i → 1 as the real system approaches the reference state. we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components
312
. Connecting with the chemical potential we saw last semester that the deviation of the chemical potential at the state of interest versus at the reference state is determined by the activity at the current state (the activity at the reference state is unity by deﬁnition). (46.Also recall that the mathematical deﬁnition of activity ai of some species i is implicitly stated as ai lim =1 (46.10)
46.12) i ai g(ζ) (46. Raoult’s Law In discussing both Raoult’s law and Henry’s law. (46. μi − μª = RT ln ai .

14) (46.16) (46. Recall that 4mix G = G(soln) − G(pure components) Hence.15) (46.18)
Now.13)
= (μ1 − μ• ) n1 + (μ2 − μ• ) n2 .For simplicity we consider here only a two component solution. Take diﬀerential change along a line of constant concentration. • ai Pi (46.
313
. so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 .17) (46. 4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46. dG = μ1 dn1 + μ2 dn2 . μ1 − μ• = RT ln 1
where Pi is the vapor pressure of the ith component above the solution. 1 2 ai low P Pi ' RT ln • .

3.26)
314
. The change in free energy upon mixing for solutions ideally obeying Raoult’s law is Ã ! • • X1 P/ X2 P/ id(RL) 1 2 4mix G = RT n1 ln + n2 ln (46. ∂T P ∂ (1/T ) P the entropy of mixing for an ideal Raoult solution is µ 4mix S = −R (n1 ln X1 + n2 ln X2 ) and the enthalpy of mixing is 4mix H = 0
id(RL) id(RL) id(RL)
(46. the vapor partial pressure of a component of a mixture is equal to the mole fraction of the component times the vapor pressure that the component would have if it were pure.20)
46.19)
(46.21)
That is.24)
(46.3.25)
(46. Ideal Solutions (RL) Raoult’s Law: Pi = Xi Pi• (46. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − .Thus
or at low P
¶ µ P1 P2 4mix G = RT n1 ln • + n2 ln • P1 P2
¶ µ a1 a2 4mix G = RT n1 ln • + n2 ln • a1 a2
(46. this is for an ideal solution in the Raoult’s Law sense.22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again.23)
(46.

28)
→ 1 as Xi → 1
Deviations from Raoult’s Law Raoult’s law is a purely statistical law. there are speciﬁc interactions between particles. and the reference state is Xi = 1 So. Since. • negative deviation: the molecules prefer to be around other types of molecules than themselves.(since G/T is independent of 1/T ). The Reference State (RL) Let us apply the deﬁnition of activity for the Raoult’s law reference state.
315
. The physical interpretation of deviation from Raoult’s law is • positive deviation: the molecules prefer to be around themselves rather than other types of molecules. in reality. real solutions generally deviate from Raoult’s law. The reference function is g(ζ) = ζ = Xi .27)
= γi
(RL)
Xi .
(46. ai =1 Xi →1 Xi lim implies ai and γ i
(RL) (RL) (RL)
(46. It does not require any kind of interaction among the constituent particle making up the solution. • no deviation: the molecules have no preference.

29)
Xi →0
Henry’s law applies to the solute not to the solvent and becomes more correct for real solution as the concentration of solute goes to zero (Xi → 0).e. Henry’s Law Henry’s Law: Pi = kXi Xi . kXi = lim µ Pi Xi ¶ (46.It is very important to note that this deviation from Raoult’s law is a property of the solution and NOT any given component. for a given component. at inﬁnite dilution. mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation. For example.3. where kXi is the Henry’s law constant.30) (46.
316
.4. i..
Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 46.

molality or molarity is used then ai and ai respectively. and the reference state is now Xi = 0 So. whereas Henry’s law applies to the subdominant species X2 → 0.31) Xi →0 Xi implies (HL) (HL) = γ i Xi . (46. they apply to opposite species in the solution. in summary • Raoult’s law: γ 1 → 1 as X1 → 1 • Henry’s law: γ 2 → 1 as X2 → 0
(HL) (HL) (HL)
= γ (HL) mi mi
(46.34)
317
. But. X1 → 1.33)
= γ Mi Mi
(HL)
(46. (HL) ai lim =1 (46. Raoult’s law applies to the dominant species. Comparison of Raoult’s Law and Henry’s Law Both Raoult’s law and Henry’s law become better approximations for real solutions as the solution becomes pure.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction.The Reference State (HL) Referring to the deﬁnition of activity again we see that the reference function is g(ζ) = ζ = Xi . So.

1. | {z }
μs 1
318
.4.4.46. Freezing Point Depression At Tf (freezing point). Colligative Properties
Colligative properties: Properties of dilute solutions that are independent of the chemical nature of the solute Examples • Freezing point depression • Boiling point elevation • Vapor pressure lowering • Osmotic pressure We will consider the examples of freezing point depression and osmotic pressure 46. μ1 (solid) = μ1 (soln).

Z Tf −4f H 4f H ln a1 ' dT = Θ. μ1 (soln) = μ• + RT ln a1 : 1 μs = μ• + RT ln a1 1 1 Rearranging this and taking the derivative with respect to T yields ¶ µ −1 ∂μs ∂μ• 1 ∂ ln a1 ∂ → 1 1 s • (μ − μ1 ) =⇒ = − ln a1 = ∂T → RT 1 ∂T RT 2 ∂T ∂T Now.Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species). The freezing point depression is
Θ=− 46.36)
= H and integrating we get µ ¶ Z → −1 4f H s • d ln a1 = (H1 − H1 ) dT = dT 2 RT RT 2 → Z Tf 4f H dT ln a1 = • RT 2 Tf
(46. T.38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf . (46. (so. dG = V dP ). using
∂μ ∂T
(46.4.35)
(46. So. Osmotic Pressure
RTf•2 ln a1 4f H
We consider the osmotic pressure at a constant temperature.2.
319
.37)
• For small changes in the freezing point we may approximate T by Tf in the integrand.

40)
(46.41)
For dilute solutions X2 is small so ln(1 − X2 ) may be expanded as ln(1 − X2 ) = −X2 + but X2 =
n2 n1 +n2 2 X3 X2 − 2 − · · · ' −X2 . Thus
1 z }| { • • V Π n1 Vm1 Π n2 . ' m1 =⇒ n2 ' n1 RT RT
V•
(46. hence ¯ μ• = μ• + RT ln a1 + V1 Π.39)
¯ where V1 is the partial molar volume of the solvent in solution (diﬃcult to measure) and Π is the hydrostatic (osmotic) pressure.43)
320
. 2 3
(46. a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) =
• Vm1 Π RT
(46. From the above equation
¯ V1 Π RT • ¯ Now we make the approximations V1 = Vm1 . 1 1 (46.42)
'
n2 n1
for dilute solutions.In the above ﬁgure μ1 (left) = μ1 (right).

V1• |{z}
'c
(46. Π=
where c is the concentration of the solute.
n2 RT = cRT.44)
Note the similarity of this equation with the ideal gas equation: P = cRT.
321
. Thus the solute in a very dilute solution behaves as if it were an ideal gas.or.

47. Entropy Production and Irreverisble Thermodynamics
We have seen that thermodynamics tells us if a process will occur and kinetics tells us how fast a process will occur. The main concept of this approach is the idea of entropy production and.
322
322
.1.
47. However. Fundamentals
We know the diﬀerence between reversible and irreversible processes from before. entropy production per unit time–how fast we are producing entropy. ultimately. we will state their respective deﬁnitions here in a manner best suited for this chapter. This allows us to make a stronger connection between thermodynamics and kinetics. These two areas of physical chemistry appear to be rather disjoint. We now we consider thermodynamics of nonequilibrium states and investigate how (and how fast) these state move towards equilibrium.

g. the one dimensional wave equation.. • di S is the change in entropy due to internal changes of the system The quantity di S is called the entropy production. • e. κ ∂t ∂x2 κ ∂(−t) ∂x2 κ ∂t ∂x2 is not invariant under time reversal.1)
We will be concerned with the change in entropy.. ∂ 2 T t→−t 1 ∂T ∂ 2T ∂2T 1 ∂T 1 ∂T = = = =⇒ =⇒ − . Deﬁnitions • de S is the change in entropy due to interactions with the exterior environment.Reversible process: dynamical equations are invariant under time inversion (t → −t).
323
. the one dimensional heat equation. c ∂t2 ∂x c ∂(−t)2 ∂x c ∂t2 ∂x is invariant under time reversal Irreversible process: dynamical equations are not invariant under time inversion (t → −t).2) (47. • e.g. which can be split into two components dS = de S + di S. 1 ∂ 2 u ∂ 2 u t→−t 1 ∂ 2 u ∂2u 1 ∂2u ∂2u = 2 =⇒ = 2 =⇒ = 2. (47. dS.

Splitting up dS into these two parts permits an easy discussion of both open and isolated systems–the diﬀerence between the two appearing only in de S. in every macroscopic region of the system the entropy production due to irreversible processes is positive.e. holds. This is simply another in our long list of alternative statements of the second law. the second law underlies all the concepts of this chapter.
324
. General criteria for irreversibility: • di S = 0 (reversible change) • di S > 0 (irreversible change) For isolated systems have di S = dS and the principle of Clausius. We need a “local” formulation of the second law: • Absorption of entropy in one part of the system. di S = dS ≥ 0. The Second Law
As you might expect.2.
47.. compensated by a suﬃcient production in another part is prohibited — i.

47. As example we now consider the last two of these: heat ﬂow and chemical reactions. phase changes. mixing.
325
.3. for example. heat ﬂow. (47.4)
¡ ¢ and the possibility of. di S I < 0 and di S II > 0 such that di S I + S II > 0 is excluded. chemical reactions. etc. Examples
The idea of entropy production can be applied to any of the processes we have talked about.I II
Considering the above ﬁgure of an isolated system.3) The local formulation statement implies di S I ≥ 0 and di S II ≥ 0 (47. we write the principle of Clausius as dS = dS I + dS II ≥ 0.

5) we get (47.47. using Qf = κA4T q =− 4t D in diﬀerential form this is
dT dq = −κA .6)
We are now interested in exposing the time dependence.
326
. (47.1. one of which is held at temperature T1 and ¯ ¯ the other at T2 (take T1 > T > T2 ) where T is the temperature at the interface.3.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II). so. Entropy Production due to Heat Flow
Recall from the lecture on transport phenomena that the heat ﬂux Qf is given by Qf = −κ 4T D
q 4t
(47.

Furthermore the heat going out of I through the connecting wall is equal to the heat coming into II through the connecting wall: di qI = −di qII . − di S = di qI T1 T2 which we see is positive because di qI < 0 when T1 > T2 .Considering the whole system dqI dqII + T1 T2
e i z }| { z }| { de qI de qII di qI di qII = + + + .8)
The quantity de qj is the amount of heat supplied by the environment to hold block j at its ﬁxed temperature.9)
(47.10)
327
. T1 T2 T1 T2
d S
dS
dS =
(47. Using this we see that the entropy production is µ ¶ 1 1 . We have still not made a connection to kinetics. To do so we must consider the entropy production per unit time
di S . dt
(47.

328
.13) dt dt ¯ Using the above expression for heat ﬂow gives us T since.V =
2. dt D So.2.P = − P − i vi μi P
i
vi μi and a ≡ − (4rxn A)T.For this example di qI di S = dt dt From chapter 24 we know
µ
1 1 − T1 T2
¶ (47. Extent of reaction: ξ is deﬁned by dξ = dni . Chemical aﬃnity: a ≡ − (4rxn G)T. − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 . T1 − T = − T − T2 ⇒ T = 2 D / D / (47.12)
¯ To determine T we use the fact that the heat ﬂow out of I is equal to the heat ﬂow into II: di qI −di qII = .3. −Aκ4T di S = dt D µ 1 1 − T1 T2
(47. (47.
47.11) ¶
−Aκ4T di qI = . where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component.14)
a result we might have guessed. Entropy Production due to Chemical Reactions Deﬁnitions: 1.

18)
d S
dS
(47.V is positive as is v..V = X
i dξ dt
dnH2 dnNH3 dnN2 = = (−1) (−3) (2)
(47. This is because a = − (4rxn A)T.15)
(47.V so
µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X
−a dξ −adξ
(47.g.19)
The entropy production per unit time for a chemical reaction is a function of both the chemical aﬃnity and of the reaction rate a dξ a di S = = v≥0 dt T dt T (47.• e.
329
. for the reaction N2 + 3H2 → 2NH3 dξ = and a = 2μNH3 − μN2 − 3μH2 The connection to kinetics: reaction rate v = The connection to thermodynamics: (dA)T.17)
z }| { z }| { (dA)T.16)
but (dA)T.20)
We see that for a spontaneous process the entropy production per unit time is positive.V dq − = (dU)T.V − T dS ⇒ dS = T T
dq
e i z}|{ z}|{ dq adξ + dS = T T
(47.

Thermodynamic Coupling
Processes may be what is called thermodynamically coupled such that a process that normally is not thermodynamically favored can be coupled to another process that is thermodynamically favored so as to allow for the unfavorable process to proceed spontaneously. (47.21) dt T j=1
The second law requires that the total entropy production for simultaneous reactions is positive. That is. a2 v2 > 0 such that a1 v1 + a2 v2 > 0. We just saw an example of such a situation with the discussion of simultaneous reactions. It says nothing about the entropy production of the individual component reactions other then the sum of all the component entropy productions must be positive.
47. diﬀusion is the ﬂux of matter down a concentration gradient.4.
For example in a system of two coupled reactions we could have a1 v1 < 0. Thermodynamic coupling need not be conﬁned to coupling between the same types of processes. Conversely.Simultaneous Reactions For N simultaneous chemical reactions. the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0. the so-called Dufour eﬀect is heat ﬂux down a concentration gradient
330
. The socalled Soret eﬀect is ﬂux of matter down a temperature gradient.

The following table lists a number of thermodynamically coupled phenomena
Flux Gradient
q
Thermoconductivity
Mechanocaloric eﬀect
m
Thermomechanical eﬀect Hydrodynamic ﬂow
material
Soret eﬀect
Reverse osmosis
Q (charge)
Seebeck eﬀect Potential of ﬂow Nernst Potential Electoconductivity
T P C ε
Dufour eﬀect Peltier eﬀect
Osmosis Electrophoresis
Diﬀusion Migration
47. Echo Phenonmena
Consider an ensemble that is perturbed away from thermal equilibrium by some means such as by applying a ﬁeld. If the perturbation is released the system will begin to evolve in time as it heads back towards the thermalized equilibrium state. • Irreversibly — The evolution towards equilibrium cannot be undone–it is irreversible Example: The spin echo in pulsed NMR • A radio frequency pulse prepares an ensemble of nuclear spins such that they are all spinning coherently. The ensemble evolves in two ways • Reversibly — A second perturbation can “undo” or reverse the evolution.5.
331
.

• The diﬀerent environment (spin frequencies) cause the ensemble spinning nuclei to dephase • Dephasing causes a decrease in the observed signal because now not all nuclei are cooperating.
332
. • Each nucleus is in a slightly diﬀerent environment so each spin frequency is slightly diﬀerent.• A strong signal is seen because all the spinning nuclei cooperate. • Now a radio pulse with the opposite phase is applied to make the nuclei spin in the opposite direction • This undoes or reverses the dephasing process and the signal regains strength • The full signal is not recovered however since all the while random thermalization is taking place to irreversibly destroy the coherence among the nuclei. • This cannot be undone with the second radio pulse.

Key Equations for Exam 4
Listed here are some of the key equations for Exam 4.
Equations
• The Clapeyron Equation is 4φ Hm dP = .23) (47. The equations are collected here simply for handy reference for you while working the problem sets.22)
333
333
.24) (47. The equations listed here are out of context and it would help you very little to memorize this section without understanding the context of these equations. This section should not substitute for your studying of the rest of this material. dT T 4φ Vm • The Clausius-Clapeyron equation is 4φ Hm d(ln P ) =− d(1/T ) R • Fick’s ﬁrst law of diﬀusion is dC 1 dn = −D A dt dx (47.

27)
• Mixing 4mix = properties of soln − • Chemical potential • Raoult’s Law: • Raoult’s law reference ai • Henry’s Law:
(RL)
properties of pure.
(47.25)
• Relation between the viscosity and the diﬀusion constant: D= kT f
f =6πηr
=
kT . ∂t ∂x
(47.33)
= γi
(HL)
Xi .31)
Pi = kXi Xi .
(47. 6πηr
(47.29)
Pi = Xi Pi•
(47. µ ¶
(47.
γi
(RL)
→ 1 as Xi → 1
(47.
γi
(HL)
→ 1 as Xi → 0.28)
μ = μª + RT ln a
(47.30)
= γi
(RL)
Xi . kXi = lim • Henry’s law reference ai
(HL) Xi →0
Pi Xi
. A dt dx X
(47.
(47.26)
• Fourier’s law of heat conduction is
dT 1 dq = Qf = −κ .32)
where kXi is the Henry’s law constant.34)
334
.• Fick’s second law of diﬀusion:
∂ 2C ∂C =D 2.

291 temperature corrected 262 atomic orbitals 49 chemists picture 50 physicists picture 50 aufbau principle 58 average value theorem 29 Berthelot gas 13. 219 jj coupling 202 LS coupling 202 quantum numbers 199. 178 partition coeﬃcient 174 Born—Oppenheimer approximation 62. 235. 311 mathematical deﬁnition of 146 activity coeﬃcient 146. 97. 312 adiabatic expansion 280 and heat capacity 280 adiabatic wall 120 angular momentum addition of 202 classical 192 eigenfunctions for 199. 124. 96.Index
absorption spectroscopy 241 activity 146. 270 binominal coeﬃcient 90 blue sky 81 Bohr model 18 335
335
Bohr radius 19 Boltzmann distribution 10. 131 bond order 77 bonding orbital 71 Born model 170 corrections to 175 enthalpy of solvation 174 entropy of solvation 174 free energy of solvation 173. 99. 219 spin 201 angular momentum quantum number 52 antibonding orbital 71 Arrhenious activation energy 261 Arrhenious equation 261. 131 Boltzmann’s equation 90. 240 and the Franck—Condon principle 243 bosons 56 Boyle temperature 272 chain rule for partial derivatives 107 character table for the C2v group 225 chemical aﬃnity 328 chemical potential 144 for a salt 161 relation to activity 148 relation to Gibbs free energy 145 relation to Helmhotz free energy 145
.

323 due to chemical reactions 328 due to heat ﬂow 326 equation of state 116 for a Berthelot gas 118 for a Dieterici gas 118 for a Redlich—Kwang gas 118 for a van der Waals gas 117 for an ideal gas 116 for gases 269 equilibrium constant 135
336
.Clapeyron equation 298. 300. 178 Debye—Huckel theory 163 Debye—Huckel—Guggenheim equation 164 Debye’s law 129. 132 enthalpy 136 entropy 105 change for changes in temperature 286 change for isothermal expansion 286 change for mixing 287 of real gases 288 entropy production 322. 291 conﬁguration 90 conﬂuent hypergeometric functions 65 correspondence principle 41 critical point 300 cyclic rule 14. 189 completeness 191 complimentary variables 30 compressibility factor at the critical point 295 compressibilty factor 270. 333 Clausius-Clapeyron equation 299. 108 cylindrical symmetry 69 Debye—Huckel limiting law 164. 231 electrolytes strong 161 electrophoretic eﬀect 167 elementary reactions 255 and stoichiometry 256 molecularity 256 emission spectroscopy 241 enemble 89 ensemble average 103. 133 degeneracy 186 of the ensemble 98 diathermic wall 120 diatomic molecules electron-electron potential energy operator for 61 electronic kinetric energy operator for 61 electronic wavefunction for 62 Hamiltonian for 61 nuclear kinetic energy operator for 61 nuclear-electron potential energy operator for 61
nuclear-nuclear potential energy operator for 61 Schrodinger equation for 62 Dieterici gas 270 diﬀusion 301 diﬀusion constant 302 eigenfunction 5 eigenvalue 5 eigenvalue equation 190 electric dipole approximation 79. 333 coeﬃcient of thermal expansion 274 coexistence curve 293 colligative properties 318 commutator 30.

334 Henry’s law constant 316. 121 intramolecular vibrational relaxation (IVR) 242
337
. 86 Hamiltonian 47 normalization constant 49. 316. 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115. 334 Franck—Condon integral 243 Franck—Condon principle 243 free energy Gibbs 138 Helmholtz 137 fugacity 147 fundamental transistions 66 general equlibrium 151 generalized displacement 110 generalized force 110 gerade 69 Gibb’s free energy 106 Gibbs-Duhem equation 163 good theory 16 group mathematical deﬁnition of 222 multiplication table 223 group theory 221 Hamiltonian operator 27 Hamitonian
classical 27 harmonic oscillator 38 energy levels for 40. 133 ﬂipping coins 90 ﬂuctuation 92 ﬂuorescence 242 stokes shift 242 Fourier’s law of heat conduction 306. 85 potential energy for 47 Schrodinger equation for 47 wavefunction (no spin) 49 wavefunction (with spin) 52 ideal solution Raoult’s law 314 immiscible solutions 153 infrared spectroscopy 66 internal energy 103.equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265. 44. 291 fermions 56 Fick’s ﬁrst law 302. 334 Hermite polynominals 40 hot bands 66 Hund’s rule 205 hydrogen atom ioniztion energy of 19 hydrogen molecule 74 hydrogenic systems 46 energy levels for 49. 333 Fick’s second law 302. 334 ﬁrst law of thermodynamics 121. 133 Heisenberg uncertainty principle 30 and the harmonic oscillator 41 helium 55 electron-electron repulsion term 55 Hamiltonian 55 Helmholtz free energy 106 Henry’s law 311.

240 force constant associated with 9 Taylor series expansion of 8 normal modes 229 operator Hermitian 189 ladder 195 linear 189 symmetry 222 operator algebra 187 orientation quantum number 53 orthogonality 191 overtone transitions 66 parameters extensive 109 intensive 109
338
. 290 mean free path 253. 86. 290 mean ionic activity 162 mean ionic activity coeﬃcient 162 method of initial velocities 259 method of isolation 259 microstate 90 Mie scattering 84 mirror plane symmetry 70 molar heat capacity 115 molecular collisions simple model for 252
molecular hydrogen ion 67 Hamiltonian for 67 molecular orbital diagram 76 molecular orbitals 68 molecular rotations 235 asymmetric tops 239 centrifugal stretching 236 linear tops 238 polyatomic molecules 237 spherical tops 239 symmetric tops 238 vibrational state dependence of 236 molecular vibrations 228 molecule Scrodinger equation for 78 momentum operator 5 Morse oscillator 64 energy levels for 65.inversion symmetry 69 operator 69 ion mobility 166 and current 168 ion transfer 174 IR spectroscopy 231 and the character table 232 isothermal compressibility 274 isothermal expansion 279 Joule expansion 282 Joule-Thomson expansion 283 kinetic theory of gases 250 Lagrange multipliers 95 Laguerre polynominals 49 laminar ﬂow 304 law of corresponding states 296 law of rectilinear diameters 293 Legendra polynomials 200 linear combinations of atomic orbitals (LCAO) 72 Lorenz number 307 many electron atom Hamlitonian for 59 maximal work 113 Maxwell relations 140 Maxwell’s distribution of speeds 252. 86 Schrodinger equation for 65 wavefunction for 65 Morse potential 64.

132 translational 101. 218 partition coeﬃcient 154 and drug delivery 155 for the Born model 174 partition function canonical 96. 248 energy 235. 132 vibrational 101. 132 Pauli exclusion principle 56 consquences of 58 perturbation theory 207 example of the quartic oscillator 208 phase diagram 300
Poiseuille’s formula 304 polarizability 79 postulate I (of quantum mechanics) 22 postulate II (of quantum mechanics) 24 postulate III (of quantum mechanics) 25 pressure 104 principle of Clausius 125. 324 principle quantum number 52 probability amplitude 22 probability distribution 22 PV work 111. 82. 133 Raman scattering 80 Raman spectroscopy 66. 181 energy levels 183 energy levels for 34.particle in a box 31. 312. 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101. 233 and the character table 234 Raoult’s law 311. 219
339
. 44. 218 features of the energy levels 35 normalization constant for 33 potenial energy 31 Schrodinger equation for 32 three dimensional 183 three dimensional energy levels 185 three dimensional wavefunction 185 wavefunction for 183 wavefunctions for 34. 276 relaxation eﬀects 167 rigid rotor 200 degeneracy of 235. 247 rotational energy levels 200. 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139. 314. 87 reaction velocity 255. 218 Hamitonian for 194 wavefunctions for 195. 44. 218 particle on a ring 194 boundary conditions 194 energy levels for 195. 334 deviations from 315 reference state 315 rate law 255 rate laws 254 determination of 258 integrated 259 Rayleigh scattering 80 Rayleigh scattering law 81.

53 spin-orbit coupling 205 Hamiltonian 205 interaction energy 205 spontaneous process 142 state function 121 table of important ones 136 Sterlings approximation 92 Stoke’s law 167. 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213. 304 STP 120 superposition 191 systems
types of 108 temperature 115 term symbols 204 thermal conductivity 301 of gases 306 of liquids 306 thermal equilibrium 120 third law of thermodynamics 128. 200 spin 201 quantum number 51. 133 statements of 127 simple collision theory 262 Slater determinant 58 for lithium 59 solar system model 17 solvation 169 solvophobic eﬀect 176 speciﬁc heat 115 spherical harmonic functions 48.degeneracy of 200 rotational Hamiltonian 200 rule of mutual exclusion 234 Rydberg constant 20 SATP 120 Schrodinger equation time dependent 214 time independent 27 second law “local” formulation 324 second law of thermodynamics 126. 219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation
340
. 53 wavefunction 51 spin orientation quantum number 51.