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

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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
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

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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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29 Addition of Angular Momentum 29.1 Spin Angular Momentum . . . . . . . . . . . 29.2 Addition of Angular Momentum . . . . . . . 29.2.1 The Addition of Angular Momentum: 29.2.2 An Example: Two Electrons . . . . . 29.2.3 Term Symbols . . . . . . . . . . . . . 29.2.4 Spin Orbit Coupling . . . . . . . . .

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201 201 202 202 203 204 205

30 Approximation Techniques 207 30.1 Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . 207 30.2 Variational method . . . . . . . . . . . . . . . . . . . . . . . . . . 209 31 The Two Level System and Quantum Dynamics 211 31.1 The Two Level System . . . . . . . . . . . . . . . . . . . . . . . . 211 31.2 Quantum Dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 214

VI

Symmetry and Spectroscopy

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32 Symmetry and Group Theory 32.1 Symmetry Operators . . . . . . . . . . . . . . . 32.2 Mathematical Groups . . . . . . . . . . . . . . . 32.2.1 Example: The C2v Group . . . . . . . . 32.3 Symmetry of Functions . . . . . . . . . . . . . . 32.3.1 Direct Products . . . . . . . . . . . . . . 32.4 Symmetry Breaking and Crystal Field Splitting

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33 Molecules and Symmetry 228 33.1 Molecular Vibrations . . . . . . . . . . . . . . . . . . . . . . . . . 228 33.1.1 Normal Modes . . . . . . . . . . . . . . . . . . . . . . . . 229 33.1.2 Normal Modes and Group Theory . . . . . . . . . . . . . . 229

34 Vibrational Spectroscopy and Group Theory 231 34.1 IR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231 34.2 Raman Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . 233 35 Molecular Rotations 35.1 Relaxing the rigid rotor . . . . . . . . . . . . . . . . . . . . . . . . 35.2 Rotational Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . 35.3 Rotation of Polyatomic Molecules . . . . . . . . . . . . . . . . . . 36 Electronic Spectroscopy of Molecules 36.1 The Structure of the Electronic State 36.1.1 Absorption Spectra . . . . . . 36.1.2 Emission Spectra . . . . . . . 36.1.3 Fluorescence Spectra . . . . . 36.2 Franck—Condon activity . . . . . . . 36.2.1 The Franck—Condon principle 235 236 236 237 240 240 241 241 242 243 243

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37 Fourier Transforms 245 37.1 The Fourier transformation . . . . . . . . . . . . . . . . . . . . . 245

VII

Kinetics and Gases

249

38 Physical Kinetics 250 38.1 kinetic theory of gases . . . . . . . . . . . . . . . . . . . . . . . . 250 38.2 Molecular Collisions . . . . . . . . . . . . . . . . . . . . . . . . . . 252 39 The Rate Laws of Chemical Kinetics 39.1 Rate Laws . . . . . . . . . . . . . . . . . . . . . . 39.2 Determination of Rate Laws . . . . . . . . . . . . 39.2.1 Differential methods based on the rate law 39.2.2 Integrated rate laws . . . . . . . . . . . . . 254 254 258 259 259

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40 Temperature and Chemical Kinetics 40.1 Temperature Effects on Rate Constants . . . . . . 40.1.1 Temperature corrections to the Arrhenious 40.2 Theory of Reaction Rates . . . . . . . . . . . . . 40.3 Multistep Reactions . . . . . . . . . . . . . . . . . 40.4 Chain Reactions . . . . . . . . . . . . . . . . . . .

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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 41.1 Equations of State . . . . . . . . . . . . . . . . . . . . 41.2 The Virial Series . . . . . . . . . . . . . . . . . . . . . 41.2.1 Relation to the van der Waals Equation of State 41.2.2 The Boyle Temperature . . . . . . . . . . . . . 41.2.3 The Virial Series in Pressure . . . . . . . . . . . 41.2.4 Estimation of Virial Coefficients . . . . . . . . . 42 Behavior of Gases 42.1 P, V and T behavior . . . . . . . . . . . . . . . . 42.1.1 α and κT for an ideal gas . . . . . . . . . . 42.1.2 α and κT for liquids and solids . . . . . . . 42.2 Heat Capacity of Gases Revisited . . . . . . . . . 42.2.1 The Relationship Between CP and CV . . 42.3 Expansion of Gases . . . . . . . . . . . . . . . . . 42.3.1 Isothermal and Adiabatic expansions . . . 42.3.2 Heat capacity CV for adiabatic expansions 42.3.3 When P is the more convenient variable . 42.3.4 Joule expansion . . . . . . . . . . . . . . . 42.3.5 Joule-Thomson expansion . . . . . . . . .

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43 Entropy of Gases 286 43.1 Calculation of Entropy . . . . . . . . . . . . . . . . . . . . . . . . 286 43.1.1 Entropy of Real Gases . . . . . . . . . . . . . . . . . . . . 288

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 44.1 Critical Behavior of fluids . . . . . . . . . . . . . . . . . . . . . 44.1.1 Gas Laws in the Critical Region . . . . . . . . . . . . . . 44.1.2 Gas Constants from Critical Data . . . . . . . . . . . . . 44.2 The Law of Corresponding States . . . . . . . . . . . . . . . . . 44.3 Phase Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . 44.3.1 The chemical potential and T and P . . . . . . . . . . . 44.3.2 The Clapeyron Equation . . . . . . . . . . . . . . . . . . 44.3.3 Vapor Equilibrium and the Clausius-Clapeyron Equation 44.4 Equilibria of condensed phases . . . . . . . . . . . . . . . . . . . 44.5 Triple Point and Phase Diagrams . . . . . . . . . . . . . . . . . 45 Transport Properties of Fluids 45.1 Diffusion . . . . . . . . . . . . . 45.2 Viscosity . . . . . . . . . . . . . 45.3 Thermal conductivity . . . . . . 45.3.1 Thermal Conductivity of 45.3.2 Thermal Conductivity of 46 Solutions 46.1 Measures of Composition . . . . 46.2 Partial Molar Quantities . . . . 46.2.1 Notation . . . . . . . . . 46.2.2 Partial Molar Volumes . 46.3 Reference states for liquids . . . 46.3.1 Activity (a brief review) 46.3.2 Raoult’s Law . . . . . . 46.3.3 Ideal Solutions (RL) . . 46.3.4 Henry’s Law . . . . . . .

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46.4 Colligative Properties . . . . . . . . . . . . . . . . . . . . . . . . . 318 46.4.1 Freezing Point Depression . . . . . . . . . . . . . . . . . . 318 46.4.2 Osmotic Pressure . . . . . . . . . . . . . . . . . . . . . . . 319 47 Entropy Production and Irreverisble Thermodynamics 47.1 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . 47.2 The Second Law . . . . . . . . . . . . . . . . . . . . . . 47.3 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . 47.3.1 Entropy Production due to Heat Flow . . . . . . 47.3.2 Entropy Production due to Chemical Reactions . 47.4 Thermodynamic Coupling . . . . . . . . . . . . . . . . . 47.5 Echo Phenonmena . . . . . . . . . . . . . . . . . . . . . 322 322 324 325 326 328 330 331

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Chemistry 351: Physical Chemistry I

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1

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. Even though there aren’t many “book” problems assigned during the year, you can still learn a lot be working these and looking that their solutions in the solution manual. Keep in mind this chapter provides some examples of how to solve problems for both physical chemistry I and physical chemistry II. Consequently early in the course some of the examples might seem very itimidating. Simply skip those examples as you scan through this chapter.

Tips for solving problems
Working problem sets is the heart and sole of learning physical chemistry. The only way that you can be sure that you understand a concept at to be able to solve the problems associated with it. This takes time and hard work. But there are some things that you can do to help yourself with these problems. Tips

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1. Remember nobody cares if you solve any particular problem on the problem set. They have all been solved before, so if you solve them you will not become famous nor will you save the world. The only reason you work them is to learn. 2. Budget your time so that you don’t have to work on an overwhelming number of problems at a time. Try to whip-off a few on the same day that you get the problem set. Then work on them consistently during the week. This will make the problem sets much more efficient at helping you learn. 3. You can do the problem. I don’t assign problems that you cannot do. If you think you can’t do the problem then maybe you need try a different way of thinking about it. 4. Part of the trouble is simply understanding what the problem is asking you to do. There is a tendency to try to start solving the problem before fully understanding the question. • Read the question carefully • Try to think about what topic(s) in lecture and in the notes the problem is dealing with. • Do not worry about not knowing how to solve it yet. • Just identify the general ideas that you think you might need. • Determine wether you need to approach the problem mathematically or conceptually or both. • If the question is long, try to identify subsections of it. 5. For problems that require a mathematical approach... • Do not be afraid. Try to figure out what mathematical techniques you need to express the solution to the problem.

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• Do the math; either you will be able to do this or you won’t. It might take some review on your part. • Always check to see if the math makes sense when you are done. 6. For problems that require a conceptual approach... • Make sure that the physical idea that you are using in your argument is correct. If you are not sure, start with a related concept that is better known by you. • Look for self-consistency. Does you final answer jive with what you know.

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). We know that this function will repeat zeros when ever sin x = 0. This occurs at x = nπ, n = 0, ±1, ±2 . . ., so the periodicity is π. The second function we should remember from trig as having a period of 2π. 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, cos 2x, has a period of π as does the imaginary part, sin 2x. Therefore the entire function has a period of π.

4

Problem: Which of the following functions are eigenfunction of the momentum d operator, px = −i~ dx . 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. If ˆ this equation is true then the function is an eigenfunction with eigenvalue λ. For the case of momentum all we need to do is take the derivative of each function, multiply by −i~ and check to see if the eigenvalue equation holds. For the first function px ψ(x) = −i~ ˆ deikx dψ(x) = −i~ = ~keikx = ~kψ(x), dx dx (2)

so, yes, this function is an eigenfunction of the momentum operator. For the second function px ψ(x) = −i~ ˆ de−αx dψ(x) ↓ 2 = −i~ = 2i~αxe−αx = 2i~αxψ(x), dx dx
2

(3)

so, no, this function is not and eigenfunction of the momentum operator. For the last function z }| { d cos kx dψ(x) = −i~ = −i~k sin kx, px ψ(x) = −i~ ˆ dx dx
6=cos kx

(4)

so, no, this function is not an eigenfunction of the momentum operator. Problem: A quantum object is described by the wavefunction ψ(x) = e−αx . What is the probability of finding the object further than α away from the origin ( x = 0)?
2

5

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. The denominator accounts for the fact that the wavefunction is unnormalized. The limits of the integral in the denominator represent all space for the object. If you were working with a normalized wavefunction the denominator would be equal to 1 and hence not needed. Plugging in the wavefunctions we have R −α −2αx2 R∞ 2 e dx + α e−2αx dx −∞ R∞ P (|x| > α) = . (6) e−2αx2 dx −∞ Mathematica can assist with these integrals to give the final answer of √ 3 P (|x| > α) = erfc[ 2α 2 ]. (7)

Solution: First of all we do not know if this wavefunction is normalized, so we should assume that it isn’t. We could normalize this wavefunction, but we won’t. 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∞ . (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. Solution: Following our general procedure from the notes if we have some unnormalized wavefunction, 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.
space

(8)

(9)

6

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 . Problem: A quantum object is described by the wavefunction ψ(x) = e−γx over the range 0 ≤ x < ∞. What is the average position of the object? Solution: We need to work with the normalized wavefunction that we found in √ the previous problem, ψ(x) = 2γe−γx . Generally and average is calculated as Z ψ∗ (x)ˆψ(x), 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 . 2γ

(13)

So on average you will find the object at x =

1 . 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 ) =

0

Z

π

0

Z

a0

|ψ1s |2 r2 sin θdrdθdφ.

(14)

Remember the extra r2 sin θ is needed when integrating in spherical polar coordinates. The normalized 1s wavefunction is 1 ψ1s = p 3 er/a0 . πa0 (15)

7

We can do this integral by hand or have Mathematica help us to give P (r > a0 ) = 5 = 0.677. e2 (16)

So, about 68% of the time the electron would be found at some distance greater then one Bohr radius from the proton. Problem: A free particle in three dimensions is described by the Hamiltonian, 2 ˆ H = −~ ∇2 . Express the wavefunction (in Cartesian coordinates) as a product 2m state. Solution: This problem appears hard at first since we are not studying three dimensional systems, but all it is asking is to express the wavefunction, which is a function of the three spatial dimensions, Ψ(x, y, z) as a product state. 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. To see this we write out the Laplacian to get µ ¶ −~2 ∂ 2 ∂2 ∂2 ˆ H= . (17) + + 2m ∂x2 ∂y 2 ∂z 2 We see that indeed the Hamiltonian is a sum of term that depends only on x, a term depending only on y and a term that depends only on z. Therefore the appropriate product state is Ψ(x, y, z) = ψ(x)ψ(y)ψ(z). (18)

Problem: Expand the Morse potential in a Taylor’s series about Req . Verify that the coefficient for the linear term is zero. What is the force constant associated with the Morse potential? Solution: The Morse potential is £ ¤ V (x) = De 1 − e−β(R−Req ) . (19)

8

So, yes the coefficient of the linear term (the term involving (R − Req ) to the first power) is zero. This will always be true when you perform a Taylor series expansion about a minimum (or maximum). The force constant is given by the coefficient of the quadratic term so in this case k = β 2 De . Problem: Without performing any calculations, 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 potential for the harmonic oscillator is described by a parabola centered about the equilibrium bond length. 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. The Morse potential does not have this symmetry. 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. 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 + · · · . (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. How many molecules are in the first excited state of the ‘ring breathing’ mode (992 cm −1 )? How

9

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. So, ¶ ³ µ ´ 3×992 992 rb × e− 2×208 × 1020 = 8.41 × 1017 Nv=1 = 2 sinh (21) 2 × 208 and
C—H Nv=1

We see that about 8.41×10 × 100% = 0.841% of the benzene molecules are in the 1020 13 first vibrational excited state for the ring breathing mode and 4.02×10 × 100% = 1020 0.0000402% of the benzene molecules are in the first excited state for the C—H stretching mode. Problem: Consider a linear chain of N atoms. Each of the atoms can be in one of three states A, B or C, except that an atom in state A can not be adjacent to an atom in state C. Find the entropy per atom for this system as N → ∞. 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, B or C. For example, ⎡ ⎤ ⎡ ⎤ ⎡ ⎤ 1 2 5 ⎢ ⎥ ⎢ ⎥ ⎢ ⎥ (1) (2) (3) (23) V = ⎣ 1 ⎦, V = ⎣ 3 ⎦, V = ⎣ 7 ⎦,··· . 1 2 5 The V (j+1) can be found from the V (j) vector using the matrix equation, V (j+1) = MV (j) , where for this example ⎤ 1 1 0 ⎥ ⎢ M = ⎣ 1 1 1 ⎦. 0 1 1 ⎡ (24)

¶ ³ µ ´ 3063 − 3×3063 2×208 × 1020 = 4.02 × 1013 . × e = 2 sinh 2 × 208
17

(22)

(25)

10

The matrix M is the so-called transfer matrix for this system. It can be shown that the number of configurations W = Tr[M N ]. Now for large N, Tr[M N ] ≈ λN , max where λmax is the largest eigenvalue of M. So W = lim λN . max
N→∞

(26)

1.

1. Use M to find V (4) 2. Verify V (3) explicitly by drawing all the allowed 3-atom configurations. 3. Verify W = Tr[M N ] for N = 1 and N = 2. 4. Use Boltzmann’s equation to find the entropy per atom for this chain as N goes to infinity.

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. 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 ⎦ . 12 5 1

.

5 states

5 states

11

States like AAC are not allowed because A and C are neighbors. For part (c) we evaluate W = Tr[M N ] for N = 1 and 2. For N = 1, W = Tr[M] = 3 This corresponds to the three distinguishable microstates A, B, and C. For N = 2, ⎤⎤ ⎡⎡ ⎤⎤ ⎤⎡ ⎡⎡ 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, AB, BA, BB, BC, CB and CC (Remember C and A cannot be neighbors). For part (d) we use S k k k = ln W = lim ln λN = lim N ln λmax = k ln λmax . max N→∞ N N→∞ N N N

(28)

So, we simply need to find the maximum eigenvalue of the Transfer matrix. Using √ Mathematica we find λmax = 1 + 2. Therefore the limiting entropy per atom is ³ √ ´ S = k ln 1 + 2 . (29) N Problem: Using the classical theory of light scattering, calculate the positions of the Rayleigh, Stokes and anti-Stokes spectral lines for benzene. 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). Solution: Since there are two vibrational modes we expect two Stokes lines to the red of 20000cm−1 , one at 20000cm−1 − 992cm−1 = 19008cm−1 and one at 20000cm−1 − 3063cm−1 = 16937cm−1 . Likewise we expect two anti-Stokes lines, one at 20000cm−1 + 992cm−1 = 20992cm−1 and one at 20000cm−1 + 3063cm−1 = 23063cm−1 . There is only one Rayleigh line and it is at the same frequency at the input laser beam which, in this case, is 20000cm−1 .

12

Problem: A simple model for a crystal is a “gas” of harmonic oscillators. Determine A, S, and U from the partition function for this model. Solution: For this model the crystal is modelled as a collection of harmonic oscillators so we need the partition function for the harmonic oscillator. Ã ! 1 N Qcrystal = qHO = (30) 2 sinh β~ω 2 From our formulas for statistical thermodynamics ¶ µ β~ω , 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, 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 . (33) ∂β 2 2 Problem: Express the equation of state for internal energy for a Berthelot gas. Solution: The equation representing a Berthelot gas is P = nRT n2 a − . V − nb T V 2 (34)

We are interesting in an equation of state for U(T, V ). Writing out the total derivative of U(T, V ) we get ¶ ¶ µ µ ∂U ∂U dT + dV. (35) dU = ∂T V ∂V T

13

¡ ¢ ¡ ∂U ¢ Now ∂U V is just heat capacity, CV , but ∂V T is nothing convenient so we must ∂T proceed. 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. One obtains ¶ µ ¶ µ n2 a n2 a ∂P nRT nR 2n2 a + 2 2 − + T −P =T = . (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

.

(40)

P

This eliminates the constant V term and so, ¶2 µ ¶ µ ∂P ∂V . Cp = Cv − T ∂T P ∂V T

(41)

14

Part I Basic Quantum Mechanics

15
15

1. Quantum Theory
The goal of science is unification. • Many phenomena described by minimal and general concepts.

1.1. 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, experiments were being performed in which the results defied explanation by means of the current understanding of physics. Among these experiments were 1. The photoelectric effect 2. Low temperature heat capacity 3. Atomic spectral lines 4. Black body radiation and the ultraviolet catastrophe 16
16

5. The two slit experiment 6. The Stern-Gerlach experiment

∗ ∗ See Handouts ∗ ∗

1.2. Bohr’s Atomic Theory
1.2.1. First Attempts at the Structure of the Atom The “solar system” model. • The electron orbits the nucleus with the attractive coulomb force balanced by the repulsive centrifugal force.

Flaws of the solar system model • Newton: OK √ √

• Maxwell: problem

17

— As the electron orbits the nucleus, the atom acts as an oscillating dipole

— The classical theory of electromagnetism states that oscillating dipoles emit radiation and thereby lose energy. — The system is not stable and the electron spirals into the nucleus. The atom collapses!

Bohr’s model: Niels Bohr (1885—1962)

18

• Atoms don’t collapse =⇒ what are the consequences Experimental clues • Atomic gases have discrete spectral lines. • If the orbital radius was continuous the gas would have a continuous spectrum. • Therefore atomic orbitals must be quantized. r=

4π 0 N 2 ~2 (1.1) Zme e2 where Z is the atomic number, me and e are the mass and charge of the electron respectively and 0 is the permittivity of free space. N is a positive real integer called the quantum number. ~ = h/2π is Planck’s constant divided by 2π.
2

The constant quantity 4π e0e~ appears often and is given the special symbol a0 ≡ m 2 4π 0 ~2 = 0.52918 Å and is called the Bohr radius. me e2 The total energy of the Bohr atom is related to its quantum number µ 2 ¶ e 1 2 . 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, i.e., N = 1 → N = ∞ µ ¶ 1 e2 −Z 2 e2 1 − 2 = (1.3) Eionize = E∞ − E1 = 2a0 ∞2 1 2a0

(1.2)

19

e — Eionize = 2a0 = 13.606 eV = 109,667 cm−1 = R. R is called the Rydberg constant.

2

— Eionize experimentally observed from spectroscopy is 13.605 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 2,3,4,· · · 3,4,5,· · · 4,5,6,· · · 5,6,7,· · · 6,7,8,· · · Series Name Lyman Balmer Pachen Brackett Pfund

(1.4)

— Since the orbitals are quantized, the atom may only change its orbital radius by discrete amounts. — Doing this results in the emission or absorption of a photon with energy v= ˜ 4E hc (1.5)

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

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

Properties of the wavefunction • Single valueness • continuous and finite • continuous and finite first derivative R • space |ψ(x, y, z)|2 dxdydz < ∞ Normalization of the wavefunction In order for |ψ(x, y, z)|2 to be exactly interpreted as a probability distribution, ψ(x, y, z) must be normalizable. qR That is, ψ unnorm = Nψnorm , where N = |ψunnorm (x, y, 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.

2.2. How to normalize a wavefunction
If we have some unnormalized wavefunction, ψunnorm we know that this function must simply be some constant N multiplied by the normalized version of this function: ψ unnorm = Nψnorm . (2.1) Now, 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. (2.2)
space space

23

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, (2.3)
space space

because that is the very definition of a normalized wavefunction. Thus wherever R we see space |ψnorm |2 dxdydz we can replace it with 1. So, Z |ψunnorm |2 dxdydz = N 2 × 1 = N 2 . (2.5)
space

Z

space

|ψnorm |2 dxdydz = 1

(2.4)

This gives us an expression for N. Taking the square root of both sides gives. sZ N=
space

|ψunnorm (x, y, z)|2 dxdydz.

(2.6)

So finally we get the normalized wavefunction by reagranging ψ unnorm = Nψnorm : ψ norm = 1 ψ . N unnorm (2.7)

Notice that no where did we ever specify what ψunnorm or ψnorm actually were, therefore this is a general procedure that will work for any wavefunction. 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 (2.8) 2 normalized x |ψ(x)| dx 1 −∞

2.3. Postulates II and II

Postulate II: Every physical observable is represented by a linear (Hermitian) operator.

24

An operator takes a function and turns it into another function ˆ Of (x) = g(x) (2.9)

This is just like how a function takes a number and turns it into another number. 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, z) and coordinate systems (spherical, cylindrical, etc.). Nearly all operators we will need are algebraic combinations of the above. Postulate III: The measurement of a physical observable will give a result that is one of the eigenvalues of the corresponding operator. There is a special operator equation called the eigenvalue equation which is ˆ Of (x) = λf (x) where λ is just a number. For a given operator only a special set of function satisfy this equation. These functions are called eigenfunctions. (2.10)

25

The number that goes with each function is called the eigenvalue. So solution of the eigenvalue equation gives a set of eigenfunctions and a set of eigenvalues. Example ˆ ˆ Let O in the eignevalue equation be the operator that takes the derivative: O = ˆ d d = dx . So we want a solution to ˆ df (x) = λf (x) df (x) = λf (x) dx (2.11)

So, we ask ourselves what function is proportional to its own derivative? ⇒ f (x) = eλx . So the eigenfunctions are the set of functions f (x) = eλx and the eigenvalues are the numbers λ

26

3. The Setup of a Quantum Mechanical Problem
3.1. The Hamiltonian
The most important physical observable is that of the total energy E. The operator associated with the total energy is called the Hamiltonian operator ˆ (or simply the Hamiltonian) and is given the symbol H. The eigenvalue equation for the Hamiltonian is ˆ Hψ = Eψ. This equation is the (time independent) Schrödinger equation. 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. (3.1)

3.2. 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. 1. Define the classical Hamiltonian for the system. 27
27

• The total energy for a classical system is Ecl = T + V, where T is the kinetic energy and V is the potential energy. • The kinetic energy is always of the form T = ¢ 1 ¡ 2 px + p2 + p2 y z 2m (3.2)

(3.3)

• The potential energy is almost always a function of coordinates only V = V (x, y, z) (3.4)

• Note: Some quantum systems don’t have classical analogs so the Hamiltonian operator must be hypothesized. 2. Use Postulate II to replace the classical variables, x, px etc., with their appropriate operators. Thus,
2 2 ˆ −~ ∇2 = −~ ∇2 , ˆ T = 2m 2m

(3.5)

where ∇2 ≡

∂2 ∂x2

+

∂2 ∂y2

+

∂2 , ∂z 2

and (3.6)

ˆ V = V (ˆ, y , z ) = V (x, y, z). x ˆ ˆ So, −~2 2 ˆ ˆ ˆ ∇ + V (x, y, z) H =T +V = 2m

(3.7)

ˆ 3. Solve the Schrödinger equation, Hψ = Eψ, which is now a second order differential equation of the form ¸ ∙ 2 −~ 2 ∇ + V (x, y, z) ψ = Eψ 2m −~2 2 ∇ ψ + (V (x, y, z) − E) ψ = 0 (3.8) ⇒ 2m

28

• Note: It is solely the form of V (x, y, z) which determines whether this is easy or hard to do. • For one-dimensional problems −~2 d2 ψ + (V (x) − E) ψ = 0 2m dx2 (3.9)

3.3. The Average Value Theorem
Postulate III implies that if ψ is an eigenfunction of a particular operator representing a physical observable, then all measurements of that physical property will yield the associated eigenvalue. However, If ψ is not an eigenfunction of a particular operator, then all measurements of that physical property will still yield an eigenvalue, but we cannot predict for certain which one. We can, however, give an expectation, or average, value for the measurement. This is given by Z hˆ i = α ψ∗ αψdxdydz ˆ (3.10)
space

For example, hˆi = x and hˆx i = p Z Z ψ xψdxdydz = ˆ

space

Z

space

x |ψ|2 dxdydz ψ∗ ∂ψ dxdydz ∂x

(3.11)

space

ψ px ψdxdydz = −i~ ˆ

Z

(3.12)

space

29

3.4. The Heisenberg Uncertainty Principle
In quantum mechanics certain pairs of variables can not, even in principle, be simultaneously known to arbitrary precision. Such variables are called complimentary. This idea is the Heisenberg uncertainty principle and is of profound importance. The general statement of the Heisenberg uncertainty principle is 1 ¯Dh ˆ iE¯ ¯ ¯ δαδβ ≥ ¯ α, β ¯ , ˆ (3.13) 2 h i ˆ means the commutator of α and β. The commutator is ˆ where the notation α, β ˆ ˆ defined as h i ˆ ≡ αβ − β α. α, β ˆ ˆˆ ˆˆ (3.14) The most important example of complimentary variables is position and momentum. We see δpx δx ≥ 1 1 |h[ˆx , x]i| = |hˆx x − xpx i| p ˆ p ˆ ˆˆ 2 ¯Z 2 ¯ µ ¶ ¯ 1¯ ¯ ψ ∗ ~ ∂ x − x ∂ ψdx¯ = ¯ 2¯ i ∂x ∂x ¯ ¯ ¯~¯ ~ = ¯ ¯= . ¯ 2i ¯ 2 (3.15)

So, at the very best we can only hope to simultaneously know position and momentum such that the product of the uncertainty in each is ~ . (n.b., δpx δy = 0, we can 2 know, for example, the y position and the x momentum to arbitrary precision.) Suppose we know the position of a particle perfectly, what can we say about its momentum?

30

4. 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. This system is very simple which is one reason for beginning with it. It also can be used as a “zeroth order” model for certain physical systems. We shall soon see that the particle in a box is a physically unrealistic system and, as a consequence, we must violate one of our criteria for a good wavefunction. Nevertheless it is of great pedagogical and practical value.

4.1. The 1D Particle in a Box Problem
Consider the potential, V (x), shown in the figure and given by ⎧ x≤0 ⎪ ∞ ⎨ V (x) = 0 0<x<a . ⎪ ⎩ ∞ x≥a

(4.1)

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.

31
31

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 2 ˆ = Eψ =⇒ −~ d ψ(x) = Eψ, Hψ 2m dx2

(4.2)

which can be rearranged into the form d2 ψ(x) 2mE + 2 ψ(x) = 0. dx2 ~ The general solution of this differential equation is ψ(x) = A sin kx + B cos kx, where k = q
2mE . ~2

(4.3)

(4.4)

Now ψ must be continuous for all x. Therefore it must satisfy the boundary conditions (b.c.): ψ(0) = 0 and ψ(a) = 0.

32

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. As can be inferred from the following figure, 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 nπx . ψn (x) = A sin a kn =

(4.5)

(4.6)

The constant A is the normalization constant. We obtain A from Z ∞ Z a nπx nπx ∗ sin dx. ψn (x)ψ n (x) = 1 = A2 sin a a −∞ 0 Letting u =
πx , a

(4.7)

du = π dx, this becomes a Z π π A2 a a/ 2a = . 1=A sin2 nudu = A2 π 0 2 / 2 π

(4.8)

33

Solving for A gives A=

r

2 . a in a box are I II III .

(4.9)

Is this wavefunction OK?

Thus our normalized wavefunctions for a particle ⎧ ⎪ 0 ⎪ q ⎨ 2 ψn (x) = sin nπx a ⎪ a ⎪ ⎩ 0 q
2mEn ~2

(4.10)

We can get the energy levels from kn = En =

and kn =

nπ : a

h n2 π 2 ~2 ~= 2π n2 h2 = . 2ma2 8ma2

(4.11)

4.2. Implications of the Particle in a Box problem
Zero Point Energy

34

The smallest value for n is 1 which corresponds to an energy of E1 = h2 6= 0. 8ma2 (4.12)

That is, the lowest energy state, or ground state, has nonzero energy. This residual energy is called the zero point energy and is a consequence of the uncertainty principle. If the energy was zero then we would conclude that momentum was exactly zero, δ p = 0. But we also know that the particle is located within a finite region of ˆ space, so δˆ 6= ∞. x Hence, δˆδp = 0 which violates the uncertainty principle. 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 (4.13)

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

ˆ The operator for kinetic energy is T =

−~ 2 d2 . 2m dx2

The important part of this is

d2 . dx2

From freshman calculus we know that the second derivative of a function describes its curvature so, a wavefunction with more curvature will have a larger second derivative and hence it will posses more kinetic energy. This is an important concept for the qualitative understanding of wavefunctions for any quantum system. 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. • We know the wavefunction is zero in regions I and III. We also know that the wave function is not zero everywhere. Therefore it must do something between x = 0 and x = a. It must have some curvature and hence some zero point energy. • As a is increased, the wavefunction is less confined and so the curvature does not need to be as great to satisfy the boundary conditions. Therefore the energy levels decrease in energy as does their difference. The particle in a box problem illustrates some of the many strange features of quantum mechanics. We have already seen such nonclassical behavior as quantized energy and zero point energy. As another example consider the expectation value of position for a particle in the second quantum level: Z ∞ Z a 2 a 2π ∗ hxi = (4.14) ψ2 (x)xψ 2 (x)dx = x sin2 [ x]dx = a 0 a 2 −∞

36

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 . 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, it can never be found at the node.

37

5. 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. We shall begin by reviewing the classical harmonic oscillator and than we will turn our attention to the quantum oscillator. The force exerted by the spring in the above figure is F = −k(R − Req ), where k is the spring constant and Req is the equilibrium position of the ball. Setting x = R − Req we can measure the displacement about the equilibrium position. 38
38

x From Newton’s law of motion F = ma = m d 2 , we get dt

2

d2 x k d2 x m 2 = −kx ⇒ 2 + x = 0 dt dt m

(5.1)

This is second order differential equation which we already know the solutions to: x = A sin ωt + B cos ωt, where ω = conditions. q
k m

(5.2)

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, we need to express the force of the spring in terms of potential energy V . We know Z 1 V = − F dx = kx2 + C. (5.3) 2 Since energy is on an arbitrary scale we can set C = 0. Thus V = 1 kx2 . 2 By postulate III the Schrödinger equation becomes ⎛ ⎞
K.E. P.E.

This can be rearrange into the form −~2 d2 ψ + 2m dx2

1 ⎜ −~2 d2 ⎟ ˆ Hψ = Eψ ⇒ ⎝ + kx2 ⎠ ψ = Eψ. 2 2 |2m dx } | {z } {z µ ¶ 1 2 kx − E ψ = 0 2

(5.4)

(5.5)

This differential equation is not easy to solve (you can wait to solve it in graduate school).

39

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. As it turns out, 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 , y = (5.6) x, An = p √ , 2 ~ 2n n! π

where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. The eigenvalues (the energy levels) are 1 En = (n + )~ω, 2 where again ω = q
k . m

(5.7)

Note the energy levels are often written as 1 En = (n + )hν 0 , 2 where ν 0 =
1 2π

(5.8)

q

k m

and is called the vibrational constant. ∗ ∗ ∗ See Fig. 11.12 Laidler&Meiser ∗ ∗∗

5.1. 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

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

41

• 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.

5.2. Spectroscopy (An Introduction)
The primary method of measuring the energy levels of a material is through the use of electromagnetic radiation. Experiments involving electromagnetic radiation—matter interaction are called spectroscopies. Atoms and molecules absorb or emit light only at specific (quantized) energies. These specific values correspond to the energy level difference between the initial and final states.

42

Key Equations for Exam 1
Listed here are some of the key equations for Exam 1. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

Equations
• The short cut for getting the normalization constant (1D, see above for 3D). sZ N=
space

|ψunnorm (x)|2 dx.

(5.9)

• The normalized wavefunction: ψ norm = 1 ψ . N unnorm (5.10)

• The Schrödinger equation (which should be posted on your refrigerator), ˆ Hψ = Eψ. (5.11)

43
43

• The Schrödinger equation for 1D problems as a differential equation, −~2 d2 ψ + (V (x) − E) ψ = 0. 2m dx2 • How to get the average value for some property (1D version), Z ψ∗ αψdx. ˆ hˆ i = α
space

(5.12)

(5.13)

• The momentum operator

px = −i~ ˆ

∂ . ∂x

(5.14)

• Normalized wavefunctions for the 1D particle in a box, r nπx 2 ψn (x) = sin . a a • The energy levels for the 1D particle in a box, En =
h n2 π 2 ~2 ~= 2π n2 h2 = . 2ma2 8ma2

(5.15)

(5.16)

• The energy level spacing for the 1D particle in a box, 4E = (2n + 1) h2 8ma2 (5.17)

• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 x, An = p ψn (y) = An Hn (y)e , y = √ , 2 n n! π ~ 2

(5.18)

where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials. r

• The energy levels are 1 En = (n + )~ω, ω = 2

k m

(5.19)

44

Part II Quantum Mechanics of Atoms and Molecules

45
45

6. Hydrogenic Systems
Now that we have developed the formalism of quantum theory and have discussed several important systems, we move onto the quantum mechanical treatment of atoms. Hydrogen is the only atom for which we can exactly solve the Schrödinger equation for. So this will be the first atomic system we discuss. The Schrödinger equation for all the other atoms on the periodic table must be solved by approximate methods.

6.1. Hydrogenic systems
Hydrogenic systems are those atomic systems which consist of a nucleus and one electron. The Hydrogen atom (one proton and one electron) is the obvious example Ions such as He+ and Li2+ are also hydrogenic systems. These system are centrosymmetric. That is they are completely symmetric about the nucleus. The obvious choice for the coordinate system is to use spherical polar coordinates

46
46

with the origin located on the nucleus. The classical potential energy for these hydrogenic systems is V (r) = So the Hamiltonian is −Ze2 . (4π 0 )r (6.1)

−Ze2 −~2 ˆ 2 ˆ . ∇ + H= 2me (4π 0 )ˆ r

(6.2)

Schrödinger’s equation (in spherical polar coordinates) becomes ˆ Eψ = Hψ (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 , 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 ¶ (6.4)

(6.5)

−~2 ˆ Hang = 2me

(6.6)

Since the Hamiltonian is the sum of two terms, ψ must be a product state. ψ(r, θ, φ) = ψrad (r)ψang (θ, φ) It turns out that solving the Schrödinger equation, ˆ Hang ψang (θ, φ) = Eψang (θ, φ), (6.8) (6.7)

47

yields ψ ang (θ, φ) = Ylm (θ, φ), (6.9)

where the Ylm (θ, φ)’s are the spherical harmonic functions characterized by quantum numbers l and m. The spherical harmonics are known functions. (Mathematica knows them and you can use them just like any other built-in function like sine or cosine.) We shall use the spherical harmonics more next semester when we develop the quantum theory of angular momentum. ˆ It also turns out that the energy associated with Hang is found to be E = El = So, l(l + 1)~2 ˆ ψang (θ, φ) Hang ψang (θ, φ) = 2me Now let’s denote the radial part of the wavefunction as ψ rad (r) = R(r). The full Schrödinger equation becomes ˆ Hψ(r, θ, φ) = Eψ(r, θ, φ) ˆ HR(r)Ylm (θ, φ) = ER(r)Ylm (θ, φ) ¶ µ 1 ˆ ˆ Hrad + 2 Hang R(r)Ylm (θ, φ) = ER(r)Ylm (θ, φ), r ˆ Operating with Hang we get ¶ µ 2 ˆ rad + l(l + 1)~ R(r)Ylm (θ, φ) = ER(r)Ylm (θ, φ) H 2me r2 (6.12) (6.11) l(l + 1)~2 . 2me (6.10)

(6.13)

48

The Ylm (θ, 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). (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). n In fact, the solutions to our differential equation are closely related to the Laguerre polynomials. µ ¶l µ ¶ 2σ 2σ −σ/n 2l+1 Rnl (σ) = Anl , (6.15) e Ln+1 n n

where the normalization constant, Anl , depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (6.16) na0 2n[(n + l)!]3 The energy eigenvalues, i.e., the energy levels are given by En = − Z 2R n2 (6.17)

Note: The energy levels are determined by n alone–l drops out. Also Note: the energy levels are the same as for the Bohr model. So, the total wavefunction that describes a hydrogenic system (ignoring the spin of the electron, which will be briefly discussed later) is ψ nlm (r, θ, φ) = Rnl (r)Ylm (θ, φ) (6.18)

6.2. Discussion of the Wavefunctions
We are now very close to having the atomic orbitals familiar from freshman chemistry.

49

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). 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. The atomic orbital you are used to from freshman chemistry are the “chemists” picture of atomic orbitals In the above table ψ1s , ψ 2s , ψ 2p0 , ψ 3d0 are pure real and so these are the same in the “chemists” picture as in the “physicists” picture. The table below lists the atomic orbitals in the “chemists” picture as linear combinations of the “physicists” picture wave functions.

50

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 )

6.3. 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, electrons also posses an intrinsic quantity called spin. Spin is actually rather peculiar so we will put off a more detailed discussion until next semester. 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). • ms is the spin orientation quantum number and ms = ±1/2 for electrons. The spin wavefunction is a function in spin space not the usual coordinate space, so we can not write down an explicit function of the coordinate space variables.

51

We simply denote the spin wavefunction generally as χs,ms and “tack it on” as another factor of the complete wavefunction. When a particular spin state is needed a further notation is commonly used: α ≡ χ 1 , 1 (the “spin-up” state) and β ≡ χ 1 ,− 1 (the “spin-down” state)
2 2 2 2

6.4. 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,l,m,s,ms = ψn,l,m χs,ms = Rnl (r)Yl,m (θ, φ)χ The energy is given by Z 2R , (6.20) n2 where recall. Again note that for a free hydrogenic system the total energy depends only on the principle quantum number n. En = − The quantum numbers of the hydrogenic system • The principle quantum number, n: determines the total energy of the systems and the atomic shells. — The principle quantum number, n, can take on values of 1,2,3. . . • The angular momentum quantum numbers, l: determines the total angular momentum of the system. It also determines the atomic sub-shells (6.19)

52

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

53

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

54

7. Multi-electron atoms
7.1. Two Electron Atoms: Helium
We now consider a system consisting of two electrons and a nucleus; for example, helium. Although the extension from hydrogen to helium seems simple it is actually extremely complicated. In fact, it is so complicated that it can’t be solved exactly. 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. 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 } , (7.1)

K.E of electron 1 K.E of electron 2 P.E of electron 1 P.E of eletcron 2

elec.—elec. repulsion

where r12 = |r1 − r2 | is the distance between the electrons.

The electron—electron repulsion term is responsible for the difficulty of the problem. It makes a closed form solution impossible. The problem must be solved by one of the following methods • Numerical solutions (we will not discuss this) 55
55

• Perturbation theory (next semester) • Variational theory (next semester) • Ignore the electron—electron repulsion (good for qualitative work only)

7.2. The Pauli Exclusion Principle
Electron are fundamentally indistinguishable. They can not truly be labelled. All physical properties of a system where we have labelled the electrons as, say, 1 and 2 must be exactly the same as when the electrons are labelled 2 and 1. Now, only |ψ|2 is directly measurable–not ψ itself. All this implies that ⎧ ⎪ +ψ(2, 1), ⎨ ψ(1, 2) = or ⎪ ⎩ −ψ(2, 1) symmetric (7.2) antisymmetric

The Pauli exclusion principle states: The total wavefunctions for fermions (e.g., electrons) must be antisymmetric under the exchange of indistinguishable fermions. Note: a similar statement exists for bosons (e.g., photons): The total wavefunction for bosons must be symmetric under exchange of indistinguishable bosons. Let us consider the two electron atom, helium

56

The total wavefunction is Ψ = ψ(1, 2)χ(1, 2) (7.3) Since a complete solution for helium is not possible we must use approximate wavefunctions. Since we are doing this, we may as well simplify matters and use product state wavefunctions (products of the hydrogenic wavefunctions). Ψ = ψ(1)ψ(2)χ(1)χ(2), | {z }| {z }
spatial part spin part

(7.4)

where the single particle wavefunctions are that of the hydrogenic system. The Pauli exclusion principle implies that if the spatial part is even with respect to exchange then the spin part must be odd. Likewise if the spatial part is odd then the spin part must be even. 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. However considering the symmetry with respect to exchange we see the following • Ψa has symmetric spatial and spin parts and is there for symmetric. It must be excluded. • Similarly for Ψd . • Ψb and Ψc have symmetric spatial parts, but the spin part is neither symmetric or antisymmetric. So, one must make an antisymmetric linear combination of the spin parts. (7.5)

57

The appropriate linear combination is α(1)β(2) − α(2)β(1). So the ground state wave function for helium is Ψg = ψ1s (1)ψ1s (2) [α(1)β(2) − α(2)β(1)] . 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 (7.7) (7.6)

7.3. Many Electron Atoms
The remaining atoms on the periodic table are handled in a manner similar to helium. Namely the wavefunction is product state that must be antisymmeterized in accordance with the Pauli exclusion principle. The product wavefunction for the ground state is determined by applying the aufbau principle. 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) . . . . . ¯ ¯ . . . . . . . . . . ¯ ¯ ¯ ¯ ¯ ψ (N)α(N) ψ (N)β(N) ψn (N )α(N) ψn (N)β(N) ¯ 1s 1s

58

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). It is also antisymmetric under exchange of columns. 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. As an example consider lithium: • There are three electrons so we need three hydrogenic wavefunctions: ψ1s α, ψ1s β, and ψ2s α (or ψ 2s β). • 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

(7.9)

(7.10)

• The short hand notation for these states is (1s)2 (2s)1 7.3.1. 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 − + (7.11) H= 2me i 4π 0 ri j>i 4π 0 rij i=1

59

8. Diatomic Molecules and the Born Oppenheimer Approximation
Now that we have applied quantum mechanics to atoms, we are able to begin the discussion of molecules. This chapter will be limited to diatomic molecules.

8.1. Molecular Energy
A diatomic molecule with n electrons requires that 3n+6 coordinates be specified. Three of these describe the center of mass position. 3n of these describe the position of the n electrons. This leaves three degrees of freedom (R, θ, φ) which describe the position of the nuclei relative to the center of mass. R determines the internuclear separation and θ and φ determine the orientation.

60
60

8.1.1. 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 . ˆ TN is the nuclear kinetic energy operator and is given by
2 2 ~2 ˆ2 ∂ ˆ2 ∂ ˆN ˆN = − ~ ∇2 = − ~ + J , R T 2μ 2μR2 ∂R ∂R 2μ

(8.1)

(8.2)
m1 m2 m1 +m2

ˆ where J is angular momentum operator for molecular rotation and μ = the reduced mass of the diatomic molecule. P ~2 ˆ 2 ˆ Te = i − 2me ∇ei is the kinetic energy operator for the electrons. ˆ VNN =
ZA ZBe e2 4π 0 R

is

is the nuclear—nuclear potential energy operator. +
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.

e2 4π 0 rji

is the electron—electron potential energy operator.

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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.

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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)

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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.

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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.

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Inversion symmetry • The potential field of the hydrogen molecular ion is cylindrically symmetric about the z-axis. • Because of the symmetry the electron density at (x, y, z) must equal the electron density at (−x, −y, −z). • The above symmetry therefore requires that the molecular orbitals be eigenfunctions of the inversion operator, ˆ. That is ı ˆψ(x, y, z) = ψ(−x, −y, −z) = aψ(x, y, z). ı • Moreover the eigenvalue a can be either +1 or −1. • 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. (9.3)

Cylindrical symmetry

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• The cylindrical symmetry implies that the potential energy can not depend on the φ. • The molecular wavefunction is described by an eigenvalue λ = 0, ±1, ±2, . . . — 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

• There is also a symmetry about the x-y plane called horizontal mirror plane symmetry: operator σ h . ˆ • Thus the molecular wavefunction must be an eigenfunction of σ h with eigenˆ value ±1. — If the eigenvalue is +1 (even with respect to σ h ) the molecular orbital ˆ is called a bonding orbital. — 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.

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

72
72

We construct two molecular orbitals as Φ+ = C+ (1sA + 1sB ) and Φ− = C− (1sA − 1sB ) The normalization condition is Z Φ± Φ± dΩ = 1 (10.4) (10.3)

(10.5)

As can be seen from the above figure, Φ+ represents a situation in which the electron density is concentrated between the nuclei and thus represents a bonding orbital. Conversely Φ− represents a situation in which the electron density is very low between the nuclei and thus represents an antibonding orbital 10.1.1. Classification of Molecular Orbitals With atoms we classified atomic orbitals according to angular momentum. 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.

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The classification according to angular momentum is as follows. λ 0 orbital symbol σ ±1 ±2 · · · π δ ···

Atomic orbitals with m = 0 form σ type molecular orbitals, e.g., s ⇒ σ, pz ⇒ σ. Those with m = ±1 form π type molecular orbitals, e.g., px ⇒ π etc. The classification according to inversion symmetry is simply a subscript “g” or “u”. For example, σ g or σ u etc. The classification according to bonding or antibonding is an asterisk is used to denote antibonding. For example, σ g is a bonding orbital and σ ∗ is an antibonding u orbital.

10.2. The Hydrogen Molecule
Let us now consider the hydrogen molecule. This molecules is a homonuclear diatomic with two electrons. If the two atoms are infinitely far apart. The ground state of the system would consist of two separate hydrogen molecules in their ground atomic states: (1s)1

74

As the atom are brought closer together, their respective s orbitals begin to overlap.

It is now more appropriate to speak in terms of molecular orbitals, so one forms linear combinations of the atomic orbitals. There are two acceptable linear combinations. These are σg = 1sA + 1sB and σ ∗ = 1sA − 1sB . u (10.7) (10.6)

75

It can be shown mathematically that the energy level associated with σg is lower than σ∗ . u We can intuit this qualitatively however since the σ ∗ orbital must have a node u whereas the σ g does not. It is also to be expected since we know H2 is a stable molecule.

10.3. Molecular Orbital Diagrams
The energy levels associated with the molecular orbitals are drawn schematically is what is called a molecular orbital diagram. The molecular orbital diagram for H2 is shown below

Molecular orbital diagrams can be drawn for any molecule. Some get very complicated. We will focus on the second row homonuclear diatomics and some simple heteronuclear diatomics.

76

The molecular orbital diagrams for the second row homonuclear diatomics are rather simple. ∗ ∗ ∗ See Supplement ∗ ∗∗ The supplement that follows this section contains examples for each of the second row 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. This disparity is not present for homonuclear diatomics. A consequence of this energy level disparity is that molecular orbitals may be formed from nonidentical atomic orbitals. For example a high lying 1s orbital may combine with a low lying 2s orbital to form a σ molecular orbital. The supplement that follows this section contains some examples of heteronuclear diatomics. Bond order • One important property that can be predicted from the molecular orbital diagrams is bond order. • Bond order is defined as BO = 1 (# of bonding electrons − # of antibonding electrons) 2 (10.8)

• Examples follow in the supplement.

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10.4. 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. Likewise we have discussed molecular orbitals which are the electronic wavefunctions. 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. (Next semester will we look at the details of this for polyatomic molecules) ˆ Hmol Ψmol = Emol Ψmol (10.9) ´ ³ ˆ ˆ ˆ Hele + Hvib + Hrot ψele ψvib ψrot = (Eele + Evib + Erot ) ψele ψvib ψrot

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11. An Aside: Light Scattering–Why the Sky is Blue
This chapter addresses the topic of light scattering from two different perspectives. • Classical electrodynamics • Classical statistical mechanics Since this is not a course on electrodynamics, we have to take several key results from that theory on faith.

11.1. 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. When the light interacts with the molecule an electric dipole is induced according to μ = αE, (11.1) where α is the polarizability of the molecule describing the “flexibility” of its electron cloud.

79
79

For light, the electric field part is E(t) = E0 cos ωt. (11.2)

The polarizability also depends on the positions of nuclei to some degree. That is, 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). 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

(11.3)

(11.4)

where a trig identity was used in the last step.

According to classical electrodynamics an oscillating dipole emits an electromagnetic field at the oscillation frequency. In this case we see the dipole oscillates at three distinct frequencies: ω, ω − ωv and ω + ω v as part of three terms in the above expression. The first term corresponds to Rayleigh scattering where the scattered light is at the same frequency as the incident light. The second term corresponds to Stokes Raman scattering where the scattered light is shifted to the red of the incident frequency.

80

The third term corresponds to anti-Stokes Raman scattering where the scattered light is shifted to the blue of the incident frequency. Classical electrodynamics can describe exactly how the oscillating electric dipole emits electromagnetic radiation. It can be shown that the emitted intensity is I= ω4 2 μ, 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. To explicitly derive this expression we would need a fair bit of electrodynamics and so the derivation is not shown here. The important point to note is that I ∝ ω 4 or alternatively I ∝ 1/λ4 . There is a very strong dependence on frequency (or wavelength). This quartic scattering dependence is, in fact, the reason why the sky is blue (from the point of view of classical electrodynamics) and is called the Rayleigh scattering law.

11.2. The Blue Sky
The spectrum of visible light from the sun incident on the outer atmosphere is essentially flat as shown below.

81

We just learned that light scatters as it traverses the atmosphere according to Rayleigh’s scattering law: I(λ) ∝ 1/λ4 .

The following figures illustrate why Rayleigh scattering implies that the sky is blue. 11.2.1. Sunsets We have focused on a blue sky, but red sunsets occur for the same reason– Rayleigh scattering.

82

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. 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.

11.2.2. White Clouds We might expect that clouds should be highly colored since they consist of droplets of water which scatter light very effectively.

83

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

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Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

Equations
• The wavefunctions for the hydrogenic system are ψnlm (r, θ, φ) = Rnl (r)Ylm (θ, φ) • The radial part is. Rnl (σ) = Anl (11.6)

µ

2σ n

¶l

e

−σ/n

2l+1 Ln+1

µ

2σ n

,

(11.7)

where the normalization constant, Anl , depends on the n and l quantum numbers as sµ ¶3 2Z (n − l − 1)! Anl = − (11.8) na0 2n[(n + l)!]3 85
85

• The energy levels for the hydrogenic system are given by En = − Z 2R n2 (11.9)

• The wavefunctions for the harmonic oscillator are ¶1 µ 2 km 4 1 − y2 ψ n (y) = An Hn (y)e , y = x, An = p √ , 2 n n! π ~ 2

(11.10)

where An is the normalization constant for the nth eigenfunction and Hn (y) are the Hermite polynomials.

• The energy levels are 1 En = (n + )~ω, ω = 2 • The Morse potential is

r

k m

(11.11)

Ee (R) = De [1 − e−β(R−Re q ) ]2 , (11.12) q μ where De is the well depth and β = 2πc˜ e 2De is the Morse parameter. ω Note: this expression for the Morse potential has the zero of energy at the bottom of the well (i.e. R = Req , ;Ee (Req ) = 0). • The Morse Potential can also be written as Ee (R) = De [e−2β(R−Req ) − 2e−β(R−Req ) ]. (11.13)

Now the zero of energy is the dissociated state (i.e. R → ∞, ;Ee (R → ∞) = 0). • The energy levels for the Morse oscillator are of the form 1 1 ω ω Evib,n = −De + hc˜ e (n + ) − hc˜ e xe (n + )2 , 2 2 where ω e xe together is the anharmonicity constant, with xe = ˜
hc˜ e ω . 4De

(11.14)

86

• 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)

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Part III Statistical Mechanics and The Laws of Thermodynamics

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88

12. Rudiments of Statistical Mechanics
When we study simple systems like a single molecule, we use a very detailed theory, quantum mechanics. However, most of the time in the real world we are dealing with macroscopic systems, say, at least 100 million molecules. It is simply impossible, even with the fastest computers, to write down and solve the Schrödinger equation for those 100 million molecules, but often Avogadro’s number of molecules. So we need a less detailed theory called statistical mechanics, which allows one to handle macroscopic sized systems without losing to much of the rigor.

12.1. 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. The systems are the same except that each one is in a different so-called microstate.

89
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• 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.

Boltzmann developed an equation to connect the microscopic properties of an ensemble to the macroscopic properties. The Boltzmann equation is S = k ln W Where S is entropy and k is Boltzmann’s constant. 12.1.1. Combinations and Permutations Consider a random system that when measured can appear in one of two outcomes (e.g., flipping coins). One valuable piece of statistical information about system is knowing how many different ways the system appears p times in, say, outcome 1 after N measurements. This is given by the mathematical formula for combinations C(N, p) = N! . p!(N − p)! (12.2) (12.1)

The number C(N, 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, p)xp .

(12.3)

90

This formula will allow us to derive a normalization constant so that we can obtain the probability of obtaining p measurements of state 1. Set x = 1 in the above. This gives (1 + 1)
N

=

N X p=0 N X p=0

C(N, p)(1)p

(12.4)

2N =

C(N, p).

So the probability of any one outcome of N measurements is P (N, p) = 1 1 N! C(N, p) = N N 2 2 p!(N − p)! (12.5)

For combinations we did not care what order the results of the measurements occurred. Sometimes the order is important. So rather than a particular combination, we are interested in a particular permutation. This is given by W (N, {Ni }) = N! N1 !N2 !N3 ! · · · (12.6)

where N is the total number of measurements and Ni is the number of indistinguishable results of type i. ∗ ∗ ∗ See Examples on Handout ∗ ∗∗ For both combinations and permutations we need to evaluated factorials.

91

This is no problem for small numbers, but when we consider macroscopic systems (1020 or so molecules) no calculator can handle factorials of such large numbers. Sterlings Approximation: • In place of evaluating factorials of large number one can use Sterling’s approximation to approximate the value of the factorial. • Sterling’s approximation is ln(N!) ' N ln N − N (12.7)

12.2. Fluctuations
When we list the macroscopic properties of a material such as a beaker of benzene or the air of the atmosphere, we speak of the average value of the property. Macroscopic equilibrium is a dynamic rather than static equilibrium. Consequently, the value of a certain property fluctuates about the average value. Often this fluctuation is not important, but sometimes it is important. The fluctuation about an average value for any observable property O is described by the variance which is defined as ¯ σ 2 ≡ O2 − O2 . O σ O is consider the range of the observable property. It can be shown that (12.8)

σO 1 ≈√ , ¯ O N where N is the number of particles. So for example if N = 1024 then

(12.9)
1 √ N

= 10−12

92

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

93

13. 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, E, and the total number of particles will be constant. The total energy is given by E=

where Ni is the number of particles in energy state i. The total number of particles is, of course, N= X
i

X
i

Ni i ,

(13.1)

Ni

(13.2)

The number of configurations for the system is then given by the number of distinct permutations of the system W = N! . 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. 94
94

For the moment let us relax the isolation constraint. Maximizing entropy corresponds to maximizing W (via S = k ln W ). This would be the situation in which every particle was in a different energy state. That is all Ni = 1 or 0. Minimizing energy would be the case where all the particles are in the ground state (say 1 ). These two situations are contradictory and some compromise must be obtained. We start by considering our original system–that being one with constant energy, 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. This is done using the mathematical technique of Lagrange multipliers (page 951 of your calc book). We will not discuss this method in detail and consequently we cannot derive the equilibrium configuration. The derivation using Lagrange multipliers arrives at the configuration in which the gi e−β i Ni = N P , (13.4) −β j j gj e | {z }
pi

where β ≡

1 kT

and gj denotes the degeneracy of states having energy

j.

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The pi represents the probability of finding the a randomly chosen particle or system which has energy i . This is the Boltzmann distribution gi e−β i Pi = P −β j gj e (13.5)

j

Since we started with a isolated system, β and hence T are constants. A given energy E will correspond to a unique temperature T. The analysis readily generalizes to variable energy i.e., nonisolated systems by considering T as a variable.

13.1. 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 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

(13.6)

and is called the canonical partition function.

96

This was first encountered as the denominator of the Boltzmann distribution and it is extremely important in statistical mechanics. (Note: the symbol Z is also often used for the canonical partition function.) The partition function is to statistical mechanics as the wavefunction is to quantum mechanics. That is, the partition function contains all that can be known about the ensemble. 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). In fact we have already seen this in the S = k ln W. But this an inconvenient connection because, for among other reasons, energy levels and temperature do not explicitly appear. 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 13.1.1. 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 ). In the following we give an argument which provides a relation between the partition functions. It is not an exact relation as we derive it, but it is a very good approximation for large numbers of particles.

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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)

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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 à #! " ¶ 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

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 n,β µ ¶ µ ¶ ∂Q 1 1 ∂ ln Q = = . βQ ∂V n,β β ∂V n,β Entropy We have already obtained the expression for entropy. It is S = U + k ln Q T µ ¶ ∂ ln Q = −kβ + k ln Q ∂β n,V (14.11) (14.10)

105

Helmholtz Free Energy Free energy is the energy contained in the system which is available to do work. That is, 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. We will make the distinction between the Helmholtz free energy and the more familiar Gibb’s free energy (G) later as well. 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 (14.12) ∂β ∂β n,V n,V = −kT ln Q Any thermodynamic property can now be obtained from the above functions as we shall see in the following chapters.

106

15. Work
We now begin the study of thermodynamics. Thermodynamics is a theory describing the most general properties of macroscopic systems at equilibrium and the process of transferring between equilibrium states. Thermodynamics is completely independent of the microscopic structure of the system.

15.1. Properties of Partial Derivatives
Of critical importance in mastering thermodynamics is to become proficient with partial derivatives. ∗ ∗ ∗ See Handout ∗ ∗∗ 15.1.1. Summary of Relations 1. The total derivative of z(x, y): µ ¶ µ ¶ ∂z ∂z dz = dx + dy ∂x y ∂y x 2. The chain rule for partial derivatives: µ ¶ µ ¶ µ ¶ ∂u ∂z ∂z = ∂x y ∂u y ∂x y 107
107

(15.1)

(15.2)

3. The reciprocal rule:

µ µ ∂z ∂x

∂z ∂x

¶ µ
y

∂x ∂z

=1 ¶

(15.3)

y

4. The cyclic rule:

y

∂z =− ∂y ∂z ∂x ¶

µ

¶ µ
x

∂y ∂x

(15.4) ¶

z

5. Finally

µ

∂z ∂x

=

u

µ

+

y

µ

∂z ∂y

¶ µ
x

∂y ∂x

(15.5)

u

15.2. Definitions
System: a collection of particles Macroscopic systems: Systems containing a large number of particles. Microscopic systems: Systems containing a small number of particles. 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. 15.2.1. Types of Systems Isolated system: A system that cannot exchange matter or energy with its environment. Closed system: A system that cannot exchange matter with its environment but may exchange energy.

108

Open system: A system that may exchange matter and energy with its environment. Adiabatic system: A closed system that also can not exchange heat energy with its environment. 15.2.2. System Parameters

Extensive parameters (or properties): properties that depend on the amount of matter. • For example, volume, mass, heat capacity. Intensive parameters (or properties): properties that are independent of the amount of matter. • For example, temperature, pressure, density. Extensive properties can be “converted” to intensive properties through ratios: Extensive property → Intensive property. Extensive property For example
mass volume

(15.6) = specific heat.

= density,

volume moles

= molar volume,

heat capacity mass

15.3. Work and Heat
A system may exchange energy with its environment or another system in the form of work or heat. • Work is exchanged if external parameters are changed during the process. • Heat is exchanged if only internal parameters are changed during the process.

109

Convention Work, w, is positive (w > 0) if work is done on the system. Work is negative (w < 0) if work is done by the system. Heat, q, is positive (q > 0) if heat is absorbed by the system. Heat is negative (q < 0) if heat is released from the system. 15.3.1. Generalized Forces and Displacements In physics you learned that an infinitesimal change in work is given by the product of force, F , times and infinitesimal change in position, dx: dw = F dx. (15.7)

For thermodynamics, we need a more general definition if infinitesimal work. Any given external parameter, A may be considered as a ‘generalized force’ which is coupled to a particular internal parameter, a, which acts as ‘generalized displacement.’ Note that the generalized force need not have units of force (e.g., Newtons) and the generalized displacement need not have units of position (e.g., meters), but the product of the two must have units of energy (e.g., Joules). The infinitesimal amount of work done on the system is then given by dw = Ada, or more generally as dw = X
i

(15.8)

Ai dai

(15.9)

110

if more than one set of parameters change. The following table gives some examples of generalized forces and displacements Generalized Force, A Generalized Displacement, a Contribution to dw Pressure, −P Stress, σ Surface tension, γ Voltage, E Magnetic Field, H Chemical Potential, μ Gravity, mg Volume, dV Strain, dε Surface area, dA Charge, dQ Magnetization, dM Moles, dn Height, dh −P dV σdε γdA EdQ HdM μdn mgdh

15.3.2. 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. That is dw = −P dV, this is called P V work. 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. (15.10)

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

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. Rx Recall from physics that work is the (path) integral over force: w = − x12 F dx. This can be manipulated as Z x2 Z x2 Z V2 F w=− F dx = − Adx = − Pex dV (15.11) 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

(15.12)

112

16. 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.

16.1. Maximal Work: Reversible versus Irreversible changes
The value of w depends on Pex during the entire expansion.

In the figure wA = −

Z

V2

V1

Patm dV = −Patm (V2 − V1 )

(16.1)

113
113

and wB = w1 + w2 , where w1 = − and Z
Vi

(16.2)

V1

Patm+2W dV = −Patm+2W (Vi − V1 ) Z
V2

(16.3)

w2 = −

Vi

Patm dV = −Patm (V2 − Vi )

(16.4)

Hence it is clear that |wB | > |wA | . Now consider case in the figure below

The expansion is reversible. That is, there is always an intermediate equilibrium throughout the expansion. Namely Pgas = Pex . So, wrev = − Z
V2

Pgas dV

(16.5)

V1

This is the limiting case of path B in the previous figure. Thus wrev is the maximum possible work that can be done in an expansion. wrev = wmax .

114

16.2. Heat Capacity
Temperature and heat are different. Temperature is not the amount of heat. Temperature is an intensive property and heat is an extensive property. However, heat is related to temperature through the heat capacity dq dT n.b., heat capacity is a function of T ; it is not a constant. C(T ) = From this equation dq = C(t)dT, (16.7) That is, when the temperature of a substance having a heat capacity C(t) is changed by dT, dq amount of heat energy is transferred. The heat capacity also depends on the conditions during the temperature change, ¡ dq ¢ ¡ dq ¢ e.g., CV (T ) = dT V and CP (T ) = dT P are not the same Heat capacity is an extensive property. To make an intensive property 1. divide by the number of moles to get molar heat capacity µ ¶ 1 dq CV m (T ) = n dT V 2. divide by mass to get specific heat 1 cV = m We will discuss heat capacity more later. µ dq dT ¶ (16.6)

(16.8)

(16.9)

V

115

16.3. Equations of State
The macroscopic properties of matter are related to one another via a phenomenological equation of state. The state of a pure, homogeneous material (in the absence of external fields) is given by the values of any two intensive properties. (More complicated systems require more than two independent variables, but behave in the same way as the more simple pure system, so we will focus our development of thermodynamics on simple systems.) The functional dependence of any property on the two independent variables is an equation of state. e.g., T , P independent then heat capacity is a function of T and P , C(T, P ). 16.3.1. Example 1: The Ideal Gas Law The equation of state for volume of an ideal gas is P V = nRT , (16.10)

where R is the gas constant (8.315 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 , (16.11) where Vm =
V . 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 (16.12)

116

16.3.2. 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. 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

In term of intensive variables P = a RT − 2. Vm − b Vm (16.14)

16.3.3. Other Equations of State The van der Waals equation of state is not the only one that has been proposed. 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 =

(16.15)

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)

(16.16)

• Redlich-Kwang P = (16.17)

118

17. The Zeroth and First Laws of Thermodynamics
Over the course of the next two lectures we will discuss the four core laws of thermodyanmics. Today we will cover the zeroth and first laws, which deal with temperature and total energy respectively. Next time we will cover the second and third laws which both deal with entropy.

17.1. Temperature and the Zeroth Law of Thermodynamics
Temperature tells us the direction of thermal energy (heat) flow. • Heat flows from high T to Low T. 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 temperature at which (for fixed V and n) the pressure is zero is defined as T =0K • T (Kelvin) = T (Celsius) + 273.15 119
119

Standard conditions • standard temperature and pressure (STP): T = 273.15 K and P = 1 atm. (Vm (STP) = 22.414 L/mol) • standard ambient temperature and pressure (SATP): T = 298.15 K and P = 1 bar. (Vm (SATP) = 24.789 L/mol)

Diathermic wall: A wall that allows heat to flow through it. Adiabatic wall: A wall the does not allow heat to flow through it. Thermal equilibrium: If two systems are in contact along a diathermic wall and no heat flows across the wall, then the systems are in thermal equilibrium. 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. (17.1)

The zeroth law implies that if an arbitrary system, C, 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.

120

17.2. 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.g., V (T, P )). The value of the state function depends only on that given state and on no other possible state of the system. 17.2.1. The internal energy state function For characterizing the change in energy of a system, one is concerned with the work done on the system (w) and the heat supplied to the system (q). The energy of a system is called the internal energy (U) of the system. The first law of thermodynamics: • Mathematical statement: or in differential form dU = dq + dw (17.3)

4U = q + w

(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.

So for a system where all the work is P V work the first law becomes Z V2 4U = q − Pex dV
V1

(17.4)

121

in differential form this is dU = dq − Pex dV (17.5)

Although U can be expressed as a function of any two state variables, the most convenient at this time are V and T. U → U(T, V ). The total differential of U (T, 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. dU = ∂T V ∂V T So, ¶ ¶ µ ∂U ∂U dq = CV dT = dq =⇒ = ∂T V ∂T V dT ¡ ¢ Hence the slope ∂U V is the heat capacity. ∂T The other slope, ¡ ∂U ¢
∂V T

(17.6)

(17.7)

µ

(17.8)

, is called the internal pressure (it has no standard symbol).

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

(17.9)

(17.10)

V

122

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

(17.11)

The equation of state for U : Express U in terms of T, V, and P. 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 ∂T ∂T ¶ ∙ µ ¸ ∂P − P dV dU = CV dT + T ∂T V

(17.12)

(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.

123

18. The Second and Third Laws of Thermodynamics
18.1. Entropy and the Second Law of Thermodynamics
We learned from statistical mechanics that entropy, S, 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. (18.1) T ¯ Now, the average energy of the system E is in fact what we call internal energy: ¯ U ≡ E. Furthermore we derived the simple relation between the Helmholtz free energy and the canonical partition function as A = −kT ln Q. Hence, U A 1 − = (U − A). T T T Since U, A, and T are state functions, S is also a state function . S= So we may write dS = (18.2)

1 (dU − dA) T 124

(18.3)

124

for an isothermal process. Recall the definition of Helmholtz free energy–the energy of the system available to do work. We learned previously that the maximum amount of work one can extract from the system is the work done during a reversible process. 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 (18.4)

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

Since U, S, T, P, and V are state functions, dU = T dS − P dV holds for any process, but in general, T dS is not heat and −P dV is not work. (see figure) T dS is heat and −P dV is work only for reversible processes.

For some dU, 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. • Case ii) P > Pex then (spontaneous) dV is positive so (P −Pex )dV is positive. • Case iii) P = Pex then (spontaneous) dV is zero so (P − Pex )dV is zero. Thus for any spontaneous process T dS ≥ dq. This is a mathematical statement of the second law of thermodynamics (18.5)

126

18.1.1. Statements of the Second Law Unlike the first law, the second law has a number of equivalent statements 1. A cyclic process must transfer heat from a hot to cold reservoir if it is to convert heat into work. 2. Work must be done to transfer heat from a cold to a hot reservoir. 3. A useful perpetual motion machine does not exist. 4. The entropy of the universe is increasing 5. Spontaneous processes are irreversible in character. 6. The entropy of an isolated system will always increase in a spontaneous process (the principle of Clausius)

18.2. The Third Law of Thermodynamics
Consider the first law for a reversible change at constant volume. dU = dq + dw = dq − Pex dV (18.6)

From our earlier discussion of heat capacity dq = CV dT (CV since constant volume). So, dU = CV dT but also dU = T dS. So CV dT =⇒ 4S = dS = T Z
T2

(18.7)

T1

CV dT. T

(18.8)

127

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 18.2.1. The Third Law Verbal statement The third law of thermodynamics permits the absolute measurement of entropy. To derive the mathematical statement of the third laws we starting with Z T2 CP dT (18.10) 4S = T T1 now let T1 → 0 4S = S2 − S0 = Z
T2

0

CP dT T

(18.11)

Hence the mathematical statement of the third law is Z T2 CP S(T2 ) = dT + S0 T 0

(18.12)

From a macroscopic point of view S0 is arbitrary. However, a microscopic point of view suggests S0 = 0 for perfect crystals of atoms or of totally symmetric molecules (e.g., Ar, O2 etc.). S0 6= 0 for imperfect crystals and crystals of asymmetric molecules (e.g., CO). Alternative statement of the third law: Absolute zero is unattainable. Consider the heat capacity near T → 0. For S0 to have significance
CP T

must be finite (not infinite) as T → 0. Thus CP → 0.

128

But CP =

dq dT

→ 0 implies

dT dq

→ ∞.

In other words, an infinitesimal amount of heat causes an infinite change in temperature.

In view of what we have learned about fluctuations, 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.

18.2.2. Debye’s Law Heat capacity data only goes down so far. So one needs a theoretical extrapolation down to T = 0. (Debye) Postulate: CP m = aT 3 . That is at low temperatures heat capacity goes as the cube of the temperature.
∗ ∗ CP m , T ∗ are the lowest temperature data points. So, a = CP m /T ∗3 .

129

The molar entropy is Sm (T ) = =

Z

18.3. Times Arrow

∗ CP C =aT 3 CP m dT P m = T T ∗3 0 ¯T ∗ ∗ ∗ CP m T 3 ¯ ¯ = CP m . T ∗3 3 ¯ 3 0

T∗

Z

T∗

T 2 dT

(18.13)

0

Entropy and the second law give a direction to time. 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. We know which picture was taken first. The interesting thing is that each molecule in a macroscopic system obeys time invariant dynamics. Both Newton’s laws and Quantum dynamics (next semester) are the same if you replace t with −t. Yet, the behavior of the macrosystem definitely changes if you replace t with −t. Thus the simple fact that you have an enormous number of particles induces a perceived asymmetry in time.

130

Key Equations for Exam 3
Listed here are some of the key equations for Exam 3. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

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.

(18.14)

(18.15)

• The canonical partition function is Q=

gj e−βEj

(18.16)

131
131

• The relation between the partition function and the molecular partition function is qN Q = mol . (18.17) N! • The Translational Partition Function V qtrans = 3 (18.18) Λ where h Λ≡ √ (18.19) 2πmkT is the thermal de Broglie wavelength. • The Rotational Partition Function (linear molecules) is T qrot ≈ , σθr
2

(18.20)

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 (18.21)

• The ensemble average of any property is given by 1 X ¯ Oi gi e−β i . O= Q i

(18.22)

• 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,V ´ ∂ ln Q = −kβ ∂β n,V ¡ ∂Q ¢ 1 1 = βQ ∂V n,β = β

³

=−

+ k ln Q ¡ ∂ ln Q ¢
∂V

³

∂ ln Q ∂β

´

n,V

n,β

132

• P V work is • Heat capacity: • General forms of the first law:

dw = −P dV. dq = C(t)dT.

(18.23)

(18.24)

4U = q + w, in differential form this is dU = dq − Pex dV. Also, dU = T dS − P dV. • The second law • The third law T dS ≥ dq. S(T2 ) = Z
T2

(18.25)

(18.26)

(18.27)

(18.28)

0

CP dT + S0 T

(18.29)

• Debye’s law for entropy at very low temperatures Sm (T ∗ ) =
∗ CP m , 3

(18.30)

∗ where CP m is the molar heat capacity at the lowest temperature for which there is data.

133

Part IV Basics of Thermodynamics

134
134

19. 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. Consequently, the concept of equilibrium plays a key role in much of what we will discuss for the remainder of the year. The equilibrium constant for a thermodynamic process, K, (which you are familiar with from general chemistry) serves are a common point which connects thermodynamics, electrochemistry, and kinetics–topics we will encounter throughout the year.

19.1. The Other Important State Functions of Thermodynamics
As was the case in quantum mechanics, here too is energy the key property with which to work. So far we have encountered two state functions which characterize the energy of a macroscopic system–the internal energy and, briefly the Helmholtz free energy.

135
135

From the first law as stated as dU = T dS − P dV (19.1)

we say that the natural (most convenient) variables for the equation of state for U are S and V . This is U = U(S, V ) Unfortunately S can not be directly measured and most often P is a more convenient variable than V Because of this fact, it is handy to define state functions which have different pairs of natural variables, so that no mater what situation arises we have convenient equations of state to work with. The other pairs of natural variables being (S and P ), (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

19.2. Enthalpy
We want a state function whose natural variables are S and P Let us try the definition H ≡ U + P V.

136

Now formally dH = dU + d(P V ) = dU + P dV + V dP, but dU = T dS − P dV, so (19.2)

/ / dH = T dS − P dV + P dV + V dP
= T dS + V dP. Hence Enthalpy does indeed have the desired natural variables. 19.2.1. Heuristic definition:

(19.3)

Enthalpy is the total energy of the system minus the pressure volume energy. So a change in enthalpy is the change in internal energy adjusted for the P V work done. If the process occurs at constant pressure then the enthalpy change is the heat given off or taken in. For example, consider an reversibly expanding gas under constant pressure (dP = 0) and adiabatic (dq = 0) conditions. The system does work during the expansion; 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. The total internal energy decreases. 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. As Freshmen we learn this as 4H = qp .

19.3. Helmholtz Free Energy
Now we want a state function whose natural variables are T and V

137

Let us try the definition A ≡ U − T S. Formally dA = dU − d(T S) = dU − T dS − SdT, but dU = T dS − P dV, so (19.4)

/ / dA = T dS − P dV − T dS − SdT
= −P dV − SdT.

(19.5)

Hence Helmholtz free energy does indeed have the desired natural variables. 19.3.1. 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.

19.4. 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. Now formally dG = dH + d(T S) = dH − T dS − SdT, but from above dH = T dS + V dP, so dG = T dS + V dP − T dS − SdT / / = V dP − SdT. Hence Gibbs free energy does indeed have the desired natural variables. (19.7) (19.6)

138

19.4.1. 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.

19.5. Heat Capacity of Gases
19.5.1. 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 (19.10) (19.9) (19.8)

The constant pressure heat capcity can then be expressed in terms of enthalpy as ¶ µ ∂H . (19.11) CP = ∂T P So, ¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V CP = = +P (19.12) ∂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 µ ∂U ∂T ¶ =
P

µ

∂U ∂T

+

V

µ

∂U ∂V

¶ µ
T

∂V ∂T

(19.13)

P

139

thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (19.14) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P . ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P . 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

(19.16)

V

Example: Ideal gases 1. 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 (19.17) ∂T P ∂T V nRT nR nR = nR = CV + T P V PV Thus CP = CV + nR or CP m = CV m + R (19.18)

19.6. The Maxwell Relations
Summary of thermodynamic relations we’ve seen so far Definitions and relations: • H = U + PV

140

• 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

20. Chemical Potential
20.1. Spontaneity of processes
Two factors drive spontaneous processes 1. The tendency to minimize energy 2. 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, (dA)T,V = dq − T dS From the second law, T dS ≥ dq for a spontaneous process, (dA)T,V ≤ 0 for a spontaneous process. Hence at equilibrium (dA)T,V = 0. 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

(20.1)

(20.2)

For constant T and P = Pex , (dG)T,P = dq − T dS Again from the second law, T dS ≥ dq for a spontaneous process, (dG)T,P ≤ 0 for a spontaneous process. Hence at equilibrium (dG)T,P = 0. So free energy provides a measure of the thermodynamic driving force towards equilibrium. Note free energy provides no information about how fast a process proceeds to equilibrium. The free energy functions are the workhorses of applied thermodynamics so we want to get a feel for them. Returning to the total differentials of free energy, dA = dU − T dS − SdT and dG = dH − T dS − SdT. (20.4) 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). Plugging these into the total differentials of free energy gives dA = −SdT − P dV and dG = −SdT + V dP (20.6) (20.5) (20.3)

143

These expressions are quite general, but i) only P V work and ii) closed systems. The total differential of A is also dA = dq + dw − T dS − SdT. For a reversible process dq = T dS and work is maximal. Hence (dA)T = dwmax =⇒ (4A)T = wmax . As we have stated in words a number of times before. The total differential of G is also dG = dq + dw + P dV + V dP − T dS − SdT. In general dw = dw0 − Pex dV where dw0 is the non-P V work. The total differential of G becomes dG = dq + dw0 − Pex dV + P dV + V dP − T dS − SdT. For constant T and P = Pex , (dG)T,P = dq + w0 − T dS. For reversible processes q = T dS and this becomes
0 0 (dG)T,P = dwmax =⇒ (4G)T,P = wmax

(20.7)

(20.8)

(20.9)

(20.10)

So, as stated earlier, the Gibbs free energy is the energy of the system available to do non-P V work.

20.2. Chemical potential
What if the amount of substance can change?

144

Extensive properties depend on the amount of “stuff” For example A(T, V ) now becomes A(T, V, n) and the total differential becomes µ ¶ ¶ µ µ ¶ ∂A ∂A ∂A dA(T, V, n) = dT + dV + dn (20.11) ∂T V,n ∂V T,n ∂n V,T Let’s focus on the slope ¡ ∂A ¢
∂n V,T

.

• 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. • Physically, this is a measure of the potential to change the amount of material. • 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, | {z }
=A

¡ ∂A ¢

∂n V,T

.

(20.12)

dG = dA + P dV + V dP

(20.13)

= −SdT − P dV + P dV + V dP + μdn / / / / = −SdT + V dP + μdn, but from dG = µ ∂G ∂T ¶ dT + µ ∂G ∂P ¶ dP + µ ∂G ∂n ¶ dn (20.14)

P,n

T,n

P,T

145

we see that μ=

µ

∂G ∂n

.

(20.15)

P,T

So, 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. The Gibbs free energy per mole (Gm ) for a pure substance is equal to the chemical potential. (Gm = μ)

20.3. Activity and the Activity coefficient
When, for example, a solute is dissolved in a solvent, there exist complicated interactions which cause deviations from ideal behavior. To account for this one must introduce the concept of activity and the activity coefficient. Activity is hard to define in words and indeed it has an awkward mathematical definition as we will soon see. 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. The mathematical definition of activity ai of some species i is implicitly stated as
ζ→ζ

lim ª

ai =1 g(ζ)

(20.16)

where g(ζ) is any reference function (e.g., pressure, mole fraction, concentration etc.), and ζ ª is the value of ζ at the reference state.

146

This implicit definition is awkward so for convenience one defines the activity coefficient as the argument of the above limit, γi ≡ which we can rearrange as ai = γ i g(ζ). (20.18) The definition of activity implies that γ i = 1 at g(ζ ª ) (the reference state) 20.3.1. Reference States Thermodynamics is founded on the concept of energy which we know to have an arbitrary scale. That is, we can define are zero of energy any where we want. Because of this it is always necessary to specify a reference state to which our real state can be compared. The choice of this state is completely up to us, but it is often the case that the reference state is chosen to be some ideal state. For example, 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. Let us consider the activity of a real gas for the above reference function and reference state. Note: the activity of gases as referenced to pressure has the special name fugacity (fugacity is a special case of activity). ai g(ζ) (20.17)

147

Our reference function is very simple: g(ζ) = ζ = P , so γ= a ⇒ a = γP. P (20.19)

Thus the activity of our real gas is given by the activity coefficient times the pressure of an ideal gas under the same conditions. 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

20.3.2. Activity and the Chemical Potential One cannot measure absolute chemical potentials, only relative potentials can be measured. By convention we chose a standard state and measure relative to that state. 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). μi − μª = RT ln ai . i (20.20)

Rather than referencing to the standard state one can also reference to any convenient “ideal” state. This ideal state is in turn referenced to the standard state. For the state of interest μi = μª + RT ln ai (20.21) i and for the ideal state μid = μª + RT ln aid ⇒ μª = μid − RT ln aid . i i i i i i (20.22)

148

Thus, μi = μid − RT ln aid + RT ln ai i i (20.23)

μi − μid = +RT ln ai − RT ln aid i i ai = RT ln id ai

Example: Real and ideal gases at constant temperature, but any pressure. Starting from the begining dμ
id

dμid = Vm dP RT dP. dμid = P

z}|{ = dGm = −Sm dT + Vm dP

=0

(20.24)

Now we integrate from the reference state to the current state of interest Z Z RT id dP. (20.25) dμ = μª Pª P This gives P . Pª The usual standard state is the ideal gas at P ª = 1, so μid − μª = RT ln μid = μª + RT ln P. (Note that as P → 1, μid → μª ). Lets say our gas is not ideal, then at a given pressure μ = μª + RT ln a. (20.28) (20.26)

(20.27)

For gases activity is usually called fugacity and given the symbol f , so a = f for real gasses. Thus μ = μª + RT ln f. (20.29)

149

Lets say that instead of referencing to the ideal gas at P = 1, we want to reference to the ideal gas at the current pressure P. This is easily done by using μª = μid − RT ln P in the above equation for μ, μ = μid − RT ln P + RT ln f f μ = μid + RT ln . P Example: The barometric equation for an ideal gas. We have an ideal gas so, μid = μª + RT ln P where we will take the reference state to be at sea level, i.e. P ª = 1 atm. So at sea level
id ª

(20.30)

and at elevation h

z }| { μ (0) = μ + RT ln 1 = μª μid (h) = μª + RT ln Ph

=0

(20.31) (20.32)

The gas fields the gravitational force which gives it a potential energy per mole of Mgh at height h. 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

(20.33)

(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.

150

21. Equilibrium
First let us consider the equilibrium A ­ B. Since A and B are in equilibrium their chemical potentials must be equal μA = μB Now, 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, if we multiply the above by n moles we have aB −4Gª = nRT ln aA as a consequence of the equilibrium condition. The quantity aB defines the equilibrium constant, Ka , for this process. aA (21.3) (21.2) (21.1)

151
151

Say the system A → B is not in equilibrium then we can not write μA = μB but we can write

Proceeding as above we get

z }| { μA + μB − μA = μB

(21.4)

μª + RT ln aA + 4μ = μª + RT ln aB A B

(21.5)

4μ = μª − μª + RT ln aB − +RT ln aA B A aB 4μ = 4μª + RT ln . aA

Again multiplying by n gives 4G = 4Gª + nRT ln aB . aA

If the 4G < 0 then the transition A → B proceeds spontaneously as written. Consider a more complicated equilibrium aA + bB ­ cC + dD. The equilibrium condition is aμA + bμB = cμC + dμD . In a manner similar to the above aμª + aRT ln aA + bμª + bRT ln aB = cμª + cRT ln aC + dμª + dRT ln aD (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

(21.6)

(21.7)

(21.9)

152

the equilibrium constant is ac ad Ka = C D =⇒ 4Gª = −RT ln Ka aa ab A B (21.10)

Note: n is absent in the above since the molar values are implied by the stoichiometry. 21.0.3. 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

, ¶

(21.11)

which is related to Ka by Ka =
0 KC

.

(21.12)

If the reactants are solutes then as the solution is diluted all the activity coefficients 0 go to unity and KC → Ka .

21.0.4. The Partition Coefficient Up to now we have only considered miscible solutions. We now consider the problem of determining the equilibrium concentrations of a solute A in both phases of an immiscible mixture.

153

The equilibrium equation is Aα ­ Aβ The equilibrium expression for this process is 4Gα→β = 0 = 4Gª − nRT ln Ka , α→β (21.14) (21.13)

where, 4Gª ≡ Gª −Gª . The equilibrium constant for this process has a special α α→β β β/α name; it is called the partition coefficient, P β/α ≡ Kpart , for species A in the α—β mixture. 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 . α aA ª

(21.15)

[A]β . [A]α

(21.16)

Knowledge of the partition function is important on the delivery of drugs because, to enter the body, the drugs must transfer between an aqueous phase and a oil phase.

154

For most drugs 0 < Ppart < 4
o/w

(21.17)

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 example, can the drug handle the acidic environment of the stomach?

155

22. Chemical Reactions
Up to now we have only been considering systems in the absence of chemical reactions. After chemical reactions take place the system is in a final “product” thermodynamic state that is in general different from the initial “reactant” state. For any extensive property • 4rxn (Property) = property of products − property of reactants • Example — Reaction: aA+bB= cC+dD — 4rxn S = cSm,C + dSm,D − aSm,A − bSm,B

22.1. 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. 4rxn H > 0 for Endothermic reactions. 156
156

(22.1)

22.1.1. Heats of Formation Hess’s Law of heat summation: 4rxn H is independent of chemical pathway Example: C2 H2 +H2 = C2 H4 . This direct reaction is not easy but it can be done in steps C2 H2 + 5 O2 → 2CO2 +H2 O(liq) 4rxn H ª = −1299.63 kJ 2 2CO2 +2H2 O(liq)→C2 H4 + 3O2 4rxn H ª = +1410.97 kJ H2 + 1 O2 →H2 O(liq) 4rxn H ª = −285.83 kJ 2 C2 H2 +H2 = C2 H4 4rxn H ª = −174.49 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. O2 , H2 , C(graphite) are examples of atoms in their natural state. Example: Formation of water • H2 + 1 O2 = H2 O not 2H2 +O2 = 2H2 O 2 • 4rxn H = ponent. P
i

ν i 4f H(i), 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 = −241.818 kJ 2 H2 + 1 O2 = H2 O(liq) 4f H ª = −285.830 kJ 2 H2 O(liq)→H2 O(gas)

4rxn H ª = −241.818 − (−285.830) = 44.012 kJ

22.1.2. Temperature dependence of the heat of reaction Z T2 4rxn CP dT 4rxn H(T2 ) = 4rxn H(T1 ) +
T1

(22.2)

157

22.2. Reversible reactions
Recall the requirement for a spontaneous change: 4G < 0 for constant T and P. 4rxn G = G(products) − G(reactants) = (remember μi = Gm,i for pure substance i). As we saw before μi can be defined in terms of activity μi = μª + RT ln ai . i So, z }| { X X ν i μª + RT ν i ln ai . 4rxn G = i
i i 4rx n Gª

X
i

ν i μi ,

(22.3)

(22.4)

(22.5)

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

(22.6)

4rxn G = 4rxn Gª + RT ln Q, where Q ≡
i

aν i is the activity quotient. i

At equilibrium, 4rxn G = 0 and Q = Ka (Thermodynamic equilibrium constant). Ka depends on T but is independent of P. For the reaction aA + bB = cC + dD Ka = ac ad C D aa ab A B (22.7)

• Note that the activity of any pure solid or liquid is for all practical purposes equal to 1.

158

• For ideal gases, 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 , a b PA PB (P ª aA )a (P ª aB )b
i

(22.8)

νi

.

So at equilibrium, 4rxn G = 4rxn Gª + RT ln Q becomes 0 = 4rxn Gª + RT ln Ka ⇒ 4rxn Gª = −RT ln Ka . (22.9)

22.3. Temperature Dependence of Ka
Starting with G =´H − T S or G/T = H/T − S. ³ From this ∂(G/T)) = H. ∂(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 , we get ¶ µ 4rxn H ª ∂ ln Ka ind. d ln Ka =− = ∂(1/T ) P of P d(1/T ) R or (using
d d(1/T )

(22.10)

(22.11)

(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

(22.13)

(22.14)

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

(22.15)

159

22.4. Extent of Reaction
There are other equilibrium “constants” that are used in the literature. • From Pj = Xj P , KX = KP P −4υg
V • From nj = Pj RT (ideal gas approximation), Kn = KP

• From concentration Cj = Equilibrium “constants” “constants” expression Ka KP KX Kn KC

nj V

=

Pj , 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. P is known when V is known and constant when concentration known

(RT )−4υg

¡ RT ¢−4υg

160

23. Ionics
Many chemical processes involve electrolytes and or acids and bases. To understand these processes we must know something about how ions behave in solution.

23.1. Ionic Activities
Consider a salt in solution Mv+ Xv− → v+ M z+ (aq) + v− X z− (aq), (23.1)

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 , ln aj = RT and ln asalt = j = + or − (23.3) (23.2)

μsalt − μª salt . RT

(23.4)

161
161

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−

(23.5)

So,

ln asalt = v+ ln a+ + v− ln a− or, alternatively, asalt = av+ av−

(23.6)

(23.7)

It is the case that 1 mole of salt behaves like v = v+ + v− moles of nonelectrolytes in terms of the colligative properties. This suggests that the interesting quantity is μsalt : v μª μsalt 1/v = salt + RT ln asalt . (23.8) v v We see that 1/v asalt = (av+ av− )1/v ≡ a± . (23.9) The quantity a± is the mean ionic activity. 23.1.1. Ionic activity coefficients The activity coefficients for ionic solutions can also be defined via a+ = γ + m+ , a− = γ − m− , where m+ = v+ m and m− = v− m. The mean ionic activity coefficient is
+ − γ ± = (γ + γ − )

(23.10)

v

v

1/v

.

(23.11)

162

The quantities a+ , a− , γ + and γ − cannot be measured individually. One can use the colligative properties to measure the ionic activity coefficients. It is convenient to redefine the osmotic coefficient as φ= −1000 g/kg ln a1 , vmM1 (23.12)

where the subscript 1 refers to the solvent. Similarly freezing point depression is redefined as θ = vφKf m. So, vφ corresponds to the empirical factor i discussed earlier. Recall how γ was calculated from the Gibbs-Duhem equation: Z m j ln γ ± = −j − dm0 , m0 0 where j = 1 − φ. (23.13)

(23.14)

23.2. Theory of Electrolytic Solutions
Ionic strength is defined as I= 1X 2 z mi , 2 i i

(23.15)

where z is the charge of the ion and m its concentration. Results from Debye—Hückel theory: point charge in a continuum The Debye—Hückel equation: √ −α |z+ z− | I √ , ln γ ± = 1 − Ba0 I

(23.16)

163

where α= e3 (εkT )3/2 B= µ 2πρ• L 1000 ¶1/2 , (23.17)

8πLe2 ρ• , (23.18) 1000εkT a0 is the radius of closest approach, e is the charge on the electron, ρ• is the density of the pure solvent, ε is the dielectric constant for the pure solvent and L is Avogadro’s number. Notice that the parameters α and B depend only on the solvent. 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. (23.19) This gives the dependence of ln γ ± for dilute solutions (m → 0). It is seen that √ the DHLL correctly predicts the m dependence of ln γ ± , which is observed exP perimentally (recall I = 1 i zi2 mi ). 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 . (23.20) v+ + v− 1− I This equation works well to ionic strengths of about I = 0.1

23.3. Ion Mobility
Current, I is given by the rate of change (in time) of charge, Q: I= dQ dt (23.21)

164

(Electrical) work, w, is required to move a change through a potential (or voltage), 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 (23.23)

Conductance is the inverse of the resistance (R−1 ). Some relevant constants • charge of an electron e = 1.602177 × 10−19 C. • Faraday’s constant F = Le = 96485 C/mol (Avogadro’s number of electrons) 23.3.1. Ion mobility

165

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 = +, −. 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, where E is the electric field, E = Also recall Newton’s law
dε . dx

(23.24)

dQi dNi = |zi | e , dt dt

(23.25)

Ni Ni dNi Avi 4t =⇒ = Avi V dt V Ni Avi V (in vacuum)

(23.26)

(23.27)

(23.28)

Fi = mai = m

dvi = zi eE. dt

(23.29)

The moving ions experience a viscous drag f that is proportional to their velocities. So the total force on the ions is a sum of the Coulomb force and the viscous drag Fi = zi eE − fvi (in solution). (23.30)

The ions quickly reach terminal velocity, i.e., the viscous drag equals the Coulomb force. Hence Fi = 0. zi eE zi eE = f vi =⇒ vi = . (23.31) f The drag f has three basic origins.

166

1. Stoke’s Law type force • “spherical” ion moving through a continuous medium • this contribution is independent of the other ions 2. Electrophoretic effect. • oppositely charged ions “pull” at each other

3. Relaxation effects • solvation shell must re-adjust as ion moves. a “dressed” ion.

167

A more fundamental quantity than ion velocity is the ion mobility, ui which is the ion’s velocity per field, vi ui = . (23.32) E For the case for parallel plate capacitors E = ε , where l is the separation of the l plates. So, vi l . (23.33) ui = ε Here the current carried by ion i is Ii = |zi | e Ni ui ε A . V l (23.34)

Suppose a salt has a degree of dissociation α (α = 1 for strong electrolytes) to produce ν + cations and ν − anions, 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 (23.35)

It is of interest to determine the ratio of the current carried by the cation versus the anion. =1 z }| { / ν +/ |z+ | u+ A / Vεl / F / ν + |z+ | u+ u+ α n I+ = = = (23.36) 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.

168

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

169
169

24.1. 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

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. • Determine the work, wdis , done in discharging the sphere. • Assume the uncharged sphere can pass from the (neutral) vacuum to the neutral solvent without doing any work, wtr = 0. (This is an approximation). • Determine the work, wch , done in charging the sphere which is now in the solvent.

171

So, 4Gv→s = wdis + wtr + wch = wdis + wch (24.1)

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.

172

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 , = − 8π 0 ri

(24.2)

where z is the oxidation state of the ion, e is the charge of the electron, ri is the radius of the sphere (ion) and 0 is the permittivity of free space. 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. So, wch = + (ze)2 8π 0 εs ri (24.3)

24.1.1. 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 (24.4)

The above expression is 4Gv→s /ion. For n moles of ions (nL = N) 4Gv→s (24.5)

173

The dielectric constant of any solvent is always greater than unity so ε1s − 1 is always negative hence 4Gv→s < 0. Thus ions always exist more stably in solution than in a vacuum.

24.1.2. 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 . 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 =

(24.6)

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

(24.7)

24.1.3. 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

From

µ

∂G ∂T

P

= −S ⇒

µ

∂4Gv→s ∂T

P

= −4Sv→s ,

(24.8)

we find entropy to be 4Sv→s ∂ =− ∂T " N (ze)2 8π 0 ri µ ¶# 1 −1 . εs (24.9)

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 ∂ . (24.10) = 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 (24.11)

24.2. 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. Unfortunately however, 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

1. The solvophobic effect: a cavity must form in the solvent to accommodate the ion. 2. 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. 3. Specific interactions: any interaction energy specific to the particular ionsolvent pair: Hydrogen bonding being the prime example. 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.

176

25. Key Equations for Exam 4
Listed here are some of the key equations for Exam 4. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

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. 177
177

dH = T dS + V dP dA = −SdT − P dV dG = −SdT + V dP

(25.1)

(25.2)

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

So, f (x) is a constant. 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, −~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. Hence we immediately have ψx = ψy ψz and Ex,nx = Ey,ny Ez,nz The total wavefunction is n2 h2 x , 8ma2 n2 h2 y = , 8mb2 n2 h2 z = . 8mc2 (26.18) nx πx 2 sin , a a r ny πy 2 sin , = b b r nz πz 2 sin = c c r (26.17) (26.16)

√ ny πy nz πz 2 2 nx πx sin sin ψ=√ sin a b c abc E = Ex,nx + Ey,ny + Ez,nz .

(26.19)

and the total energy is (26.20)

185

Degeneracy The 3D particle in a box model brings up the concept of degeneracy. When n(> 1) states have the same total energy they are said to be n-fold degenerate. Let the 3D box be a cube (a = b = c) then the states (nx = 2, ny = 1, nz = 1), (nx = 1, ny = 2, nz = 1), (nx = 1, ny = 1, nz = 2) have the same total energy and thus are degenerate. (26.21)

186

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

— 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. e.g., " #" # " # 1 0 3 1 3 1 = (27.1) 2 1 1 1 7 3 but " 3 1 1 1 #" 1 0 2 1 # " 5 1 3 1 # " 3 1 7 3 #

=

6=

(27.2)

Algebraic rules for operators 1. Equality: ˆ if α = β, then αf (x) = g(x) = βf (x) ˆ ˆ ˆ 2. Addition: ˆ if αf (x) = g(x) and βf (x) = h(x), ˆ ˆ ˆ then (ˆ + β)f (x) = αf (x) + βf (x) = g(x) + h(x) α ˆ 3. Multiplication: ³ ´ ˆ (x) = α βf (x) ˆ αβf ˆ ˆ (27.5) (27.4) (27.3)

ˆˆ ˆ α β αf (x) = β (ˆ f (x)) , ˆˆ but in general αβf (x) 6= β αf (x). ˆˆ 4. 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 (27.6)

188

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), and ˆ ˆ ˆ — α(λf (x)) = λˆ f (x), where λ is a complex number. 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. • 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, −y, −z) ı ı ´ ³ ˆ ∇f(x, y, z) = ∂ ex + ∂ ey + ∂ ez f(x, y, z) ˆ • ∇: ∂x ∂y ∂z ´ ³ 2 2 2 ∂ ∂2 ∂2 ˆ ˆ • ∇ : ∇ f (x, y, z) = ∂x2 + ∂y2 + ∂z2 f (x, y, z)

¡d

dx

¢ f (x) =

d2 f (x) dx2

Commutators: We have seen that in general αβ 6= β α. This leads to the construction of the ˆˆ ˆˆ commutator, [◦, ◦]: h i ˆ ≡ αβ − β α. α, β ˆ ˆˆ ˆˆ (27.7)

189

h i ˆ = β α, then α, 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), then the operator equation, αf (x) = g(x) ˆ ˆ becomes the eigenvalue equation αf (x) = af (x). ˆ (27.8)

The eigenvalue equation is of fundamental importance in quantum theory. We shall see that eigenvalues of certain operator can be identified as experimental observables. Commuting operators and simultaneous sets of eigenfunctions. ˆ ˆ If αf (x) = af (x) and β and α commute, then βf (x) = bf (x). ˆ ˆ The proof goes as follows: On the one hand, ˆ α ˆ ˆ β (ˆ f ) = β (af) = aβf because f is an eigenfunction of α. ˆ On the other hand, ³ ´ ˆ α β (ˆ f ) = α βf ˆ ˆ ³ ´ ³ ´ ˆ α βf = a βf . ˆ ˆ (27.9)

(27.10)

ˆ because β and α commute. ˆ Thus

(27.11)

ˆ which states that βf is an eigenfunction of α with eigenvalue a. The only way for ˆ ˆ = bf. this to be true is if βf

190

27.2. Orthogonality, Completeness, and the Superposition Principle
Theorem 1: The eigenfunctions of a Hermitian operator corresponding to different eigenvalues are orthogonal: Z ψ∗ ψk = 0, j 6= k. (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 (27.13)
i

191

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

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; simplifying gives l = −l0 Thus mmax = l, mmin = −l and so m = l, l − 1, l − 2, . . . , −l + 1 , −l. This also implies that the number of ‘rungs’ is 2l + 1 and that l must be either an integer or a half-integer. (28.48) (28.45)

and

(28.46)

substituting in the relation we just found for k gives

(28.47)

28.5. Quantum Properties of Angular Momentum
The eigenfunctions of angular momentum are entirely specified by two quantum numbers l and m: ψlm . ˆ L2 ψlm = l(l + 1)ψ lm ˆ Lz ψlm = mψ lm (28.49)

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, φ). (28.51)

199

The spherical harmonics are functions of two variables, but they are a product of a function only of θ and a function only of φ, ψlm = Ylm (θ, φ) = APl (θ)eimφ ,
|m| |m|

(28.52)

where the Pl (θ) are the Legendra polynomials and A is normalization constant. Both the spherical harmonics and the Legendra polynomials are tabulated. They are also built-in functions of Mathematica. The spherical harmonics (and hence the angular momentum wavefunctions) are orthonormal; meaning, ( Z 2π Z π 1 l0 = l and m0 = m (28.53) Yl∗m0 (θ, φ)Ylm (θ, φ) sin θdθdφ = 0 0 l0 6= l or m0 6= m 0 0 28.5.1. The rigid rotor Rotational energy For general rotation in three dimensions the is ~2 ˆ ˆ H = L2 , 2I so the Schrödinger equation is ~2 ˆ ~2 ˆ Hψ lm = Elm ψlm ⇒ L2 ψlm = Elm ψlm ⇒ l(l + 1)ψlm = Elm ψlm . 2I 2I Thus Elm = (28.55) (28.54)

l(l + 1)h2 l(l + 1)~2 = = El . (28.56) 2I 8π2 I There is no m dependence for the energy. In other words, the energy levels are determined only by the value of l. We know that there are 2l + 1 different m values for a particular l value. All 2l + 1 of these wavefunctions correspond to the same energy. We say the there is a 2l + 1 degeneracy of the energy levels.

200

29. Addition of Angular Momentum
29.1. Spin Angular Momentum
We learned above that l may take on integer or half-integer values. Systems in which l takes on half-integer values are peculiar. These systems have no classical analogs. One example of such a system is the spin of an electron, l = s = 1/2. The values of m = ms are limited to +1/2 and −1/2. One peculiarity of this system is that the wavefunctions are 4π periodic (and 2π antiperiodic): ψs (θ) = −ψs (θ + 2π) (29.1) and ψ s (θ) = ψs (θ + 4π). (29.2)

That means that the system has to ‘rotate’ twice (in spin space not coordinate space) to get back to its original state. ∗ ∗ ∗ See in-class demonstration: the belt trick ∗ ∗∗

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29.2. 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. One measures, however, the total angular momentum, J. The electrons in many electron atoms couple. The are two main coupling schemes which account for the total angular momentum of the atom. 1. 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,max , (Ms = i msi ) P • find the total orbital angular momentum L = Mmax , (M = i mi ) • then J = L + S 2. 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 . • we will not use this method. 29.2.1. 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; we use J when we speak generally.)

202

ˆ ˆ ˆ The total angular momentum is JT = J1 + J2 . 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 (29.3)

We need to determine the allowed values of the total angular momentum quantum number J. The maximum value of J is determined by the maximum value of M by Jmax = Mmax = m1max + m2max = j1 + j2 (29.4)

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, Jmin = |j1 − j2 | . (29.5)

The total angular momentum is quantized is exactly the same manner as any other angular momentum. Thus the allowed values of J are J = j1 + j2 , j1 + j2 − 1, . . . , |j1 − j2 | + 1, |j1 − j2 | . 29.2.2. An Example: Two Electrons The table below shows the total spin angular momentum S for a two electron system (29.6)

203

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, gS , of the states is given by 2S + 1. In the above example the degeneracy is gS = 3 for the S = 1 states and gS = 1 for the S = 0 states. 29.2.3. Term Symbols We have already seen several term symbols, those being 1 S and 3 S during our discussion of helium. Term symbols are simply shorthand notion used to identify states. Term symbols are useful for predict and understanding spectroscopic data. So, it is worthwhile to briefly discuss them. 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). The orbital degeneracy is given by gL = 2L + 1. For historical reasons L values are associated with a letter like the l values of a hydrogenic system are. L 0 symbol S 1 P 2 D 3 F 4 5 . G H

204

The term symbol for a particular states is constructed from the following general template gS LJ . Many electron atoms have term symbols associated with their states. Rules: 1. All closed shells have zero spin and orbital angular momentums: L = 0, S = 0. These states are all singlet S states, notated by 1 S 2. An electron and a “hole” lead to equivalent term symbols. • E.g., p1 and p5 have the same term symbol. 3. Hund’s Rule for the ground state only. 1. The ground state will have maximum multiplicity. 2. If several terms have the same multiplicity then ground state will be that of the largest L. 3. Lowest J value (regular) “electron”, Highest J value (inverted) “hole” 29.2.4. Spin Orbit Coupling A charge possessing angular momentum has a magnetic dipole associated with it. An electron has orbital and spin magnetic dipoles. These dipoles interact with a certain spin—orbit interaction energy ESO . The spin—orbit Hamiltonian is [ ˆ HSO = hcAL · S ´ ³ ˆ ˆ ˆ ˆ SO = hcA J 2 − L2 − S 2 , H 2 (29.7)

205

where A is the spin—orbit coupling constant. From the Hamiltonian the spin—orbit interaction energy is ESO = hcA [J(J + 1) − L(L + 1) − S(S + 1)] 2 (29.8)

206

30. Approximation Techniques
As we learned last semester, there are very few models for which we can obtain an exact solution. Consequently we must be satisfied with using approximation methods. Last semester, we always took the simplest approximation to give the qualitative properties of the unsolvable system. Now we will consider two important quantitative approximation methods: (i) perturbation theory and (ii) variational theory

30.1. Perturbation Theory
The basic procedure of perturbation theory • Find a solvable system that is similar to the system at hand. • 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.

207
207

• The first order energy is then used to make a first order approximation to the wavefunction. • The procedure is repeated to get higher and higher order approximations. This process get algebraically intensive so we will only go as far as listing the first order energy correction. The nth state energy in perturbation theory:
(0) (1) En = En + En + . . . , (0)

(30.1)
(1)

where En is the nth state energy for the unperturbed (solvable) system and En is the first order correction. This is given by Z (1) ˆ En = ψ(0)∗ H (1) ψ(0) dx, (30.2) n n
all space

ˆ where H (1) is the first order correction to the Hamiltonian–the perturbation. 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. • The obvious solvable system is the harmonic oscillator: 1 ~2 d2 ˆ + kx2 . H=− 2 2m dx 2 (30.3)

• The perturbative part of the Hamiltonian is ˆ H (1) = ax4 .

√ 2 This has energy levels En = ~ω(n+ 1 ) and wavefunctions An Hn ( αx)e−αx /2 , 2 q where α = km ~ (30.4)

208

• For example, the ground state energy correction is then calculation from Z ∞ (1) (0)∗ ˆ (0) ψ0 H (1) ψ0 dx (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 = , 5 4α 2 so the first order ground state energy for a quartic oscillator is √ ~ω 3 πaA2 0 + E0 ' . 5 2 2 4α

30.2. Variational method
The basic idea behind the variational method is to use a trial wavefunction with an adjustable parameter. The value of the parameter which minimizes the energy, Etrial , gives a trial wavefunction which is closest to the real wavefunction. The basis for this is the variation theorem which states Etrial ≥ E. We will not prove this theorem here. The trial energy is calculated by Etrial = R R
all space

ˆ ψ∗ Hψtrial dx trial ψ∗ ψtrial dx trial (30.6)

all space

The trial energy is now a function of the adjustable parameter, p, that we use to minimize the trial energy by setting dEtrial =0 dp (30.7)

209

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

210

31. The Two Level System and Quantum Dynamics
Our entire discussion of quantum mechanics thus far had dealt only with time independent quantum mechanics. The time variable never appears in any expression. Obviously there are cases where quantum objects move with time. For example, firing an electron down a particle accelerator. We shall finally get to quantum dynamics in this chapter, but first we will discuss the very important model of the two level system.

31.1. The Two Level System
If the harmonic oscillator is the most important model in all a physics, the two level system is a close second. The spin system discussed above is an example of a two level system. The two level system is inherently quantum mechanical in nature. Unlike the harmonic oscillator it has no classical analogue.

211
211

Consequently, we can not use our usual procedure of writing down the classical Hamiltonian and then replacing the variables with their corresponding operators. 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 , 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 ). i=1 The states ψ 1 and ψ2 are eigenfunctions of the two level Hamiltonian, ˆ H=
1 δ 1,°

+ 2 δ 2,° ,

(31.2)

where δ j,° “projects out” the j th state of the wavefunction being acted on.

212

For example let some arbitrary wavefunction ψ = aψ 1 + bψ2 , then ˆ Hψ = ( 1 δ 1,° + =
1 δ 1,° 2 δ 2,° ) (aψ 1

+ bψ2 )
2 δ 2,°

(31.3)

(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 (31.4)

(31.5)

states.

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 . 2 2 (31.6)

(31.7)

213

31.2. Quantum Dynamics
So far we have been concerned with the eigenfunctions and eigenvalues (energy levels) of the various quantum systems that we have discussed. What has been kept hidden up to now is the fact that the eigenfunctions are really multiplied by a phase factor of the form . Ψn (x, t) ≡ ψn (x)e− ~ En t
i

(31.8)

We can verify this by obtaining the time independent Schrödinger equation from the more general time dependent ∂Ψn (x, 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)
i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i ˆ = Hψn (x)e− ~ En t i

(31.9)

ˆ En ψn (x)e− ~ En t = e− ~ En t Hψn (x) ˆ En ψn (x) = Hψ n (x)

(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. This is given by ¯Z ¯2 ¯ ¯ ∗ P (x, t) = ¯ Ψn (x, 0)Ψn (x, t)dx¯ (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,
214

so no matter what time t we check we will always find the system in the same eigenstate. Thus the eigenstates are stationary states. In general the state of the system need not be in one particular eigenstate; it may be in a superposition of any number of eigenstates. The “left” and “right” wavefunctions that we saw in the discussion of the two level system are examples of superposition states. The phase factor does become important for superposition states. As an example consider the state 1 1 Φ(x, t) = √ Ψ1 (x, t) + √ Ψ2 (x, t) 2 2 exposing the phase factors we get
i i 1 1 Φ(x, t) = √ ψ1 (x)e− ~ E1 t + √ ψ2 (x)e− ~ E2 t 2 2

(31.12)

(31.13)

Let’s now track the probability of finding the particle in the same superposition state. Similar to before we calculate ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x, 0)Φ(x, t)¯ P (x, 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 à ! ¯2 i i ¯ ¯1 ψ ∗ (x)ψ 1 (x)e− ~ E1 t + ψ∗ (x)ψ 2 (x)e− ~ E2 t ¯ ¯ 1 1 dx¯ . = ¯ (31.14) 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

integrated because the eigenfunctions are orthogonal. This leaves ¯2 ¯Z ¯ ¯ ¯ Φ∗ (x, 0)Φ(x, t)¯ (31.15) P (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 . +e +1 = = 4 2 ~ The probability of find in the system in its original superposition states is not one for all times t.

216

Key Equations for Exam 1
Listed here are some of the key equations for Exam 1. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

Equations
• The short cut for getting the normalization constant . sZ N=
space

|ψunnorm (x, y, z)|2 dxdydz.

(31.16)

• The normalized wavefunction: ψnorm = 1 ψ . N unnorm (31.17)

• How to get the average value for some property, Z ψ∗ αψdxdydz. ˆ hˆ i = α
space

(31.18)

217
217

• The Laplacian

∇ =

2

µ

∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z

.

(31.19)

• Normalized wavefunctions for the 3D particle in a box, √ ny πy nz πz nx πx 2 2 sin sin . sin ψn (x) = √ a b c abc • The energy levels for the 3D particle in a box, Enx ,ny ,nz • Orthonormality: Z n2 h2 n2 h2 n2 h2 y x = + + z 2. 8ma2 8mb2 8mc (

(31.20)

(31.21)

ψ∗ ψk j

=

space

1, 0,

j=k . j 6= k

(31.22)

• 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 , Ly = i~Lz , ˆ y , Lz = i~Lx , ˆ z , Lx = i~Ly (31.24) L L L and h i h i h i ˆ 2 , Lx = L2 , Ly = L2 , Lz = 0. ˆ ˆ ˆ ˆ ˆ L m2 h2 ~2 m2 = . 2I 8π2 I (31.25)

• The energy levels for a particle in a ring are Em =

(31.26)

• The normalized wavefunctions for a particle on a ring are 1 ψ = √ eimφ . 2π (31.27)

218

• The eigenfunctions of angular momentum are entirely specified by two quantum numbers l and m: ψ lm . ˆ L2 ψlm = l(l + 1)ψ lm • The energy levels for the rigid rotor are El = l(l + 1)~2 . 2I (31.29) ˆ Lz ψlm = mψ lm (31.28)

• Degeneracy for general angular momentum is gJ = 2J + 1. • The first order energy correction in pertubation theory is Z (1) ˆ ψ(0)∗ H (1) ψ(0) dx, En = n n
all space

(31.30)

(31.31)

• 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

(31.32)

• In general

Ψn (x, t) ≡ ψn (x)e− ~ En t

i

(31.33)

• The left and right superposition states are 1 1 ψL = √ ψ1 + √ ψ2 2 2 and 1 1 ψR = √ ψ1 − √ ψ2 2 2 (31.34)

(31.35)

219

Part VI Symmetry and Spectroscopy

220
220

32. Symmetry and Group Theory
We now take a short break from physical chemistry to discuss ideas from the mathematical field of group theory. Inherent to group theory is symmetry. As far as we are concerned, we will • determine the symmetry of a particular molecule. • The types of symmetry it has will determine to which symmetry group it belongs. • 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

32.1. Symmetry Operators
Any operator that leaves |ψ|2 invariant are symmetry operators for that particular system: ˆ O |ψ|2 = |ψ|2 . (32.1) This implies ˆ Oψ = ±ψ. That is, the eigenvalues for the particular symmetry operator are 1 or −1. For molecules we will be dealing with point group symmetry operators. These operators deal with symmetry about the center of mass. We have seen two such operators in ˆ and σ h . 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. This type of operator arrises in the treatment of extended crystal structures. ∗ ∗ ∗ See Handout on Symmetry Elements ∗ ∗∗ (32.2)

32.2. Mathematical Groups
In mathematics the term “group” has special meaning. It is a set of objects and a single operation, which has the following properties. 1. The group is associative (but not necessarily communative) with respect to the operation. 2. An identity element exits and is a member of the group

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3. The “product” of any two members of the group yield a member of the group. 4. The inverse of every member of the group is also in the group. In other words, for any member of the group one can find another member of the group which, upon “multiplication,” yields the identity element.

∗ ∗ ∗ See Handout on Naming Point Groups ∗ ∗∗ ∗ ∗ ∗ See Handout on Assigning Point Groups ∗ ∗∗ Associated with a given group is a “multiplication” table. 32.2.1. Example: The C2v Group ˆ ˆ ˆ The C2v group consists of the symmetry elements E, C2 , σ v (in-plane) and σ 0v ˆ (transverse). 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

32.3. Symmetry of Functions
In the absence of degeneracy, the wavefunctions must be symmetric or antisymmetric with respect to all elements of the group.

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Connecting with the C2v group example lets consider the wavefunctions for water. In this case one can collect the eigenvalues (either +1 or −1) for each of the four symmetry operators as a four component vector. As it turns out there is four possible sets of eigenvalues–hence four different vectors: A1 = (1, 1, 1, 1) A2 = (1, 1, −1, −1) B1 = (1, −1, 1, −1) B2 = (1, −1, −1, 1). To see where these four vectors come from, consider the following. 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. 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.

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The above considerations leave four vectors. In fact, there will always be the same number of vectors as symmetry elements. Altogether, the vectors represent what is call an irreducible representation of the group. 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 ∗ ∗∗ 32.3.1. Direct Products The direct product of a two vectors is defined as (x1 , x2 , x3 , . . .) ⊗ (y1 , y2 , y3 , . . .) = (x1 y1 , x2 y2 , x3 y3 , . . .) For the example of the C2v group consider B1 ⊗ B2 = (1, −1, 1, −1) ⊗ (1, −1, −1, 1) = (1, 1, −1, −1) = A2 (32.4) (32.3)

32.4. 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.

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

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The D vector has a degeneracy of five and the symmetry of 2z 2 − x2 − y 2 , xz, yz, xy, x2 − y 2 . 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. The F states have a degeneracy of 7 and the symmetry of z 3 , xz 2 , yz 2 , xyz, z(x2 − y 2 ), x(x2 − 3y 2 ) and y(3x2 − y 2 ). In an octahedral environment the states split with one becoming A2 , 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 octahedral group is still highly symmetric. Lets say that two atoms on opposite sides of the cube are moved slightly inward. The remaining four atoms remain in place. This breaks the octahedral symmetry and the system now assumes D4 symmetry. Now the A1 vector of the O group becomes the A1 vector of the D4 group. The triply degenerate T1 vector splits into a A2 state and a doubly degenerate E state. The E states from the O group become a A1 type state and a B1 type state. The T1 states from the O group become a A2 type state and a E type state. The T2 states from the O group become a B2 and a E type state.

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33. Molecules and Symmetry
From our chapter on diatomic molecules last semester we have learned a great deal which caries over directly to polyatomic molecules. So, in this chapter we simply investigate some of the specific details regarding polyatomic molecules.

33.1. Molecular Vibrations
As for diatomic molecules, it is convenient to work with center of mass coordinates. With polyatomic molecules one needs to specify the coordinates of N nuclei rather than just two nuclei. To do so we begin with the 3N nuclear degrees of freedom. As for the diatomic case 3 degrees of freedom determine the center of mass motion. That leaves us with 3N − 3 coordinates to specify. One must now consider two different types of polyatomic molecules: Linear and Nonlinear. • 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.

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33.1.1. Normal Modes Polyatomic molecules can undergo very complicated vibrational motion. Regardless of what type of vibrational motion is taking place, however, that motion is some linear combination of fundamental vibrational motions called normal modes. This is analogous to writing an arbitrary wavefunction as a linear combination of eigenfunctions. One example was the “left” and “right” states of the two level system. The number of normal modes equals the number of vibrational degrees of freedom. At low energies the normal modes are well approximated as harmonic oscillators.

33.1.2. 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. Example: Water The point group symmetry of the water molecule is C2v . 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. The three modes are the bending vibration, the symmetric stretching vibration and the asymmetric stretch.

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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. For the bending mode, the vibration is complete unchanged by any of the symmetry elements. Consequently the bending mode is associated with A1 The same is true for the symmetric stretching mode. It too is associated with A1 . ˆ The asymmetric stretch, however, is associated with B1 since C2 and σ0v transform ˆ the mode into its opposite and σ v leaves it unchanged. ˆ

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34. Vibrational Spectroscopy and Group Theory
We now investigate how group theory and, in particular, the character tables can be used to determine IR and Raman spectra and selection rules for polyatomic molecules

34.1. IR Spectroscopy
IR absorption is exactly the same as regular electronic absorption except the frequency of the electromagnetic radiation is much less. The typical “energies” for IR absorption are from 400 to 4000 cm−1 . This is in the Infrared region of the electromagnetic spectrum. As for electronic absorption one typically employs the electric dipole approximation. The electric dipole approximation • Molecule is viewed as a collection of charges • Multipole expansion monopole + dipole + quadrapole+ · · · 231
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(34.1)

• Light—matter interaction is dominated by the light—dipole coupling so the other interactions are ignored. In order for absorption of the electromagnetic radiation to take place, it must be able to couple to a changing (oscillating) electric dipole. The electric dipole is μ = μx ex + μy ey + μz ez where μx = qx, μy = qy, μz = qz. 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, y, or z for the particular group. Example: Water Recall that the point group symmetry of the water molecule is C2v . We now need a column of the character table which we have ignored up to this point. The character table is C2v A1 A2 B1 B2 ˆ E ˆ C2 σv ˆ σ 0v ˆ Functions (34.2)

1 1 1 1 z, x2 , y 2 , z 2 1 1 −1 −1 xy 1 −1 1 −1 x, xz 1 −1 −1 1 y, yz

The last column describes the symmetry of several important functions for the point group.

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Among these functions are x, y, and z. So we can see immediately that the IR active modes of any molecule having this point group will be A1 , B1 , and B2 . 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). From before we know the modes of water have A1, and B1 symmetry and hence are all IR active and appear in the IR spectrum

34.2. 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. The light loses energy to the material in an amount equal to the vibrational energy of the molecules is the sample. This lose of energy shows up in the scattered light as a new down shifted frequency from that of the original input light frequency. Unlike IR absorption which is based on the electric dipole, 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.

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

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35. Molecular Rotations
Recall that the three degrees of freedom that described the position of the nuclei about the center of mass were (R, θ, φ). The R was involved in vibrations. We now turn our attention to the angular components to describe rotations. 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 . (35.1) R 2μ 2μR2 ∂R ∂R 2μ We will now be concerned only with the angular part, ~2 ˆ2 (35.2) J . 2I Now, under the Born-Oppenheimer approximation, R is a parameter. For constant R the rotational energy is given by − Erot = J(J + 1)~2 J(J + 1)h2 . = 2μR2 8π 2 I (35.3)

This is the so-called rigid rotor energy. It is common to define Be ≡ as the rotational constant. Then Erot = J(J + 1)hBe with a degeneracy of gJ = 2J + 1 235
235

h 8π 2 I

(35.4)

(35.5)

(35.6)

35.1. Relaxing the rigid rotor
Of course the rigid rotor is not a perfectly correct model for a diatomic molecule. There are two corrections we will now make 1. Vibrational state dependence: • The R value is dependent on the particular vibrational level. • One defines a rotational interaction constant that depends on the vibrational level, n. ¶ µ 1 Bn ≡ Be − n + αe , (35.7) 2 where αe is an empirical rotational—vibrational interaction constant. 2. Centrifugal stretching: • Rotation tends to stretch the diatomic distance R. • This is corrected for by the term −J 2 (J + 1)2 Dc , where Dc ≡
3 4Be ω2 ˜e

(35.8)

(35.9)

is the centrifugal stretching constant.

35.2. Rotational Spectroscopy
A rotational transition can occur in the same vibrational level n. This is called a pure rotational transition. Alternatively, a rotational transition can accompany a vibrational transition. In either case the selection rule for the transition is 4J = ±1.

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It turns out that typical rotational energy gaps are on the order of a few wavenumbers or less. Thermal energy, kT, at room temperature is about 200 cm−1 . This means that at room temperature the many excited rotational states are populated. ∗ ∗ ∗ See Handout ∗ ∗∗ The selection rules and the thermalized states combine to yield a multi-peaked ro-vibrational spectrum. ∗ ∗ ∗ See Handout ∗ ∗∗

35.3. 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. The principle axes coordinate system is the one in which the z-axis is taken to be along the principle symmetry axis. The total moment of inertia, 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

(35.10)

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There are four classes of polyatomic molecules regarding rotations 1. Linear (e.g., carbon dioxide) • Izz = 0, Ixx = Iyy ˆ ˆ2 ˆ2 • J 2 = Jx + Jy • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1), where B= 2. Symmetric tops (e.g., benzene) • Ixx = Iyy h 8π2 Ixx (35.12)

~2 ˆ2 ˆ J H= 2Ixx

(35.11)

(35.13)

ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is # " ˆ2 ˆ2 ˆ2 ~2 Jx + Jy Jz ˆ + H= 2 Ixx Izz

(35.14)

• The rotational energy is Erot = hBJ(J + 1) + h(A − B)K 2 , where A= (35.15)

h , (35.16) 8π 2 Izz h (35.17) B= 2 8π Ixx and K is the quantum number describing the projection of the angular momentum onto the z-axis

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3. Spherical tops (e.g., methane) • Ixx = Iyy = Izz

ˆ ˆ2 ˆ2 ˆ2 • J 2 = Jx + Jy + Jz • The Hamiltonian is • The rotational energy is Erot = hBJ(J + 1), where B= h 8π2 Ixx (35.19) ~2 ˆ2 ˆ J H= 2Ixx (35.18)

(35.20)

4. Asymmetric tops • Ixx 6= Iyy 6= Izz • These are more complicated and we will not discuss them in detail

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36. Electronic Spectroscopy of Molecules
The electronic spectra of molecules are quite different than that of atoms. Atomic spectra consist of single sharp lines due to transitions between energy levels. Molecular spectra, on the other hand, have numerous lines (bands) due to the fact that electronic transitions are accompanied by vibrational and rotational transitions.

36.1. 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. We found that in doing so the electronic energy level, Ee , was parameterized by the internuclear distance, R. Ee as a function of R describe the effective potential for the nuclei. It had a qualitative shape similar to the Morse potential.

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In the figure below the ground and first excited electronic levels (as a function of R) are shown. Note: The potential minima are not at the same value of R for each of the electronic states.

36.1.1. Absorption Spectra In absorption spectroscopy, 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. ∗ ∗ ∗ See Spectroscopy Supplement p1 ∗ ∗∗ 36.1.2. Emission Spectra In emission spectroscopy, 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.

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∗ ∗ ∗ See Spectroscopy Supplement p2 ∗ ∗∗ 36.1.3. Fluorescence Spectra All during the process of absorption, the process of is taking place. ∗ ∗ ∗ 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. 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. • This process is called • The molecule than emits a photon to drop back down into an excited vibrational state of the ground electronic state. • This requires a lower energy (or “more red”) photon. Hence the Stokes shift.

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36.2. 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, but we will ingore this). Assuming the electronic transition is allowed one must calculate the probability of the vibrational transistion as well. This is down by evaulating the Franck—Condon integral.

36.2.1. The Franck—Condon principle When the Born—Oppenheimer approximation is applied to spectroscopic transitions, one obtains the Franck—Condon principle. The Franck—Condon principle states that the nuclei do not move during an electronic transition. 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. Mathematically this means that the strength of a transition from Ψi = ψel,i ψvib,i → Ψf = ψel,f ψvib,f is given by ¯Z ¯ ¯ ¯ ¯ ¯2 ¯Z ¯ ¯ ¯ ¯ Ψ∗ μel Ψi ¯ = ¯ ˆ f ¯ ¯ Z ¯2 ¯ ¯ ψ∗ ψ∗ μel ψel,i ψvib,i ¯ , ˆ el,f vib,f ¯ (36.1)

all space

el space

vib space

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

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37. Fourier Transforms
As a spectroscopist it is imperative to have a deep understanding of the relationship between time and frequency. 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, 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. Furthermore, if the signal decays rapidly it will have a broad spectrum and, conversely, if the signal decays slowly it will have a narrow spectrum. The mathematics which governs these qualitative statements is Fourier transform theory which we now review.

37.1. The Fourier transformation
The Fourier transformation, =, of a function f (t) will, in this work, by denoted ˜ by a tilde, f (ω), and is given by Z ∞ ˜(ω) = = [f (t)] = f f(t)eiωt dt. (37.1)
−∞

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The Fourier transformation is unique and it has a unique inverse, =−1 , which is given by Z ∞ h i 1 −1 ˜ ˜ = (37.2) f(ω)e−iωt dω. f (ω) = f (t) = 2π −∞ The above two relations form the convention used throughout this work. Other authors use different conventions, so one must take care to know exactly which convention is being used. For simplicity the symbol = will be used to represent the Fourier transformation ˜ operation, i.e., = [f (t)] = f (ω). Whereas the symbol =−1 will represent the inverse h i −1 ˜ Fourier transformation, i.e., = f(ω) = f(t).

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Key Equations for Exam 2
Listed here are some of the key equations for Exam 2. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

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. 247
247

(37.3)

h 8π 2 I

(37.4)

• The degeneracy of the rigid rotor is gJ = 2J + 1 • Franck—Condon Factor: ¯Z ¯ ¯ ¯ ¯ ¯2 ¯ ¯ ψ∗ ψvib,i ¯ vib,f ¯ Z

(37.5)

vib space

(37.6)

• The Fourier transformation is

˜ = [f (t)] = f (ω) =

f (t)eiωt dt.

(37.7)

−∞

• The inverse Fourier transformation is Z ∞ h i 1 −1 ˜ ˜ = f(ω)e−iωt dω. f (ω) = f (t) = 2π −∞

(37.8)

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Part VII Kinetics and Gases

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38. Physical Kinetics
We now turn our attention to the molecular level and in particular to molecular motion.

38.1. kinetic theory of gases
A microscopic view of gases Consider a gas of point mass (m), m is the molecular (or atomic) mass • Each particle of mass m has velocity v, hence a momentum of p = mv and a kinetic energy of KE = 1 mv · v = 1 mv 2 . 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 . V

(L is Avogadro’s number):

Consider the ith particle at position xi = (x, y, z) in coordinate (position) space. ¡ ¢ Its velocity is vi = dxi = dxi , dyi , dzi . This can represented in velocity space by dt dt dt dt the vector vi = (vxi , vyi , vzi ). The velocities of the particles are characterized by a probability distribution function for velocities F (vx , vy , vz , t) which is in general a function of time, t. 250
250

The number of particles, NVv , having velocities in a macroscopic volume, Vv , in velocity space is Z Z Z Z NVv = N F (v, t)dv = N F (vx , vy , vz , t)dvx dvy dvz (38.1)
Vv Vv

It is more convenient to switch to spherical polar coordinates in velocity space (v, θ, φ); n.b., v is simply a magnitude (not a vector)–it is the speed.

The probability distribution function then becomes F (v, θ, φ, t) If we choose the origin of our coordinate system to be at the center of mass of the gas, then for many cases the velocity distribution will be isotropic–independent of θ and φ. F (v, θ, φ, t) = F (v, t). (38.2) Furthermore, stationary distributions–those independent of time–are often encountered. F (v, θ, φ, t) = F (v, θ, φ). (38.3)

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We shall consider stationary isotropic distributions F (v). So F (v) represents a distribution of speeds. It can be shown from first principles that µ ¶3 2 −mv 2 m F (v) = 4π e 2kb T v 2 (38.4) 2πkb T where kb = 1.380658 × 10−23 is Boltzmann’s constant. This is the Maxwell’s distribution (of speeds).

38.2. 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( (38.5) 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. For an ideal gas (V = P ), n = = RT . n RT |{z}
=L

A simple model for molecular collisions:

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• 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. ∗ ∗ ∗ See Handout ∗ ∗∗ • The number of collisions equals the number of particles with their centers in V : number of collisions = n∗ πσ 2 v4t (38.6) • The collision frequency = n∗ πσ 2 v For the above model we need to find the average collision frequency. 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 . ¯ 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

(38.8)

Example: Ar at SATP (T = 298 K, P = 1 bar): v = 380.48 ¯ m , s

collision = 5.25 × 109 s−1 , frequency λ = 72.5 nm

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39. The Rate Laws of Chemical Kinetics
Thermodynamics described chemical systems in equilibrium. For the study of chemical reactions it is important understand systems that can be very far from equilibrium. For this we turn to the field of chemical kinetics. We can, from thermodynamics, address the question; Will the reaction occur? We need kinetics, however, answer the question: How fast will the reaction occur?

39.1. Rate Laws
Consider a general four component reaction aA + bB = cC + dD (39.1)

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. That is, d[B] d[C] d[D] d[A] or − or or (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, in general, equal b. We must account for the stoichiometry.

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We define the reaction velocity as v= 1 d[I] vi dt (39.3)

where vi = −a, −b, c or d and I = A, B, C, 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 + (39.4) 0 B0 → c0 C0 + d0 D0 b A rate law is the mathematical statement of how the reaction velocity depends on concentration. v = f (conc.) (39.5) For the most part, rate laws are empirical. Many, but certainly not all, rate laws are of the form v = k[A1 ]xA 1 [A2 ]xA 2 · · · [An ]xA n . (39.6)

The reaction is said to be of order xAi in species Ai and it is of overall order P i xA i . 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

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Let 2A + 2B = C + D be the overall reaction. One possible set of elementary steps could be elementary rxn A + A → A0 A00 + 2B→ C + D A0 → A00 molecularity Bimolecular Unimolecular Trimolecular . (39.8)

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] . 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, rate laws for overall reactions can not be determined by stoichiometry. Connection to thermodynamics Consider the overall or elementary reaction aA + bB ­ cC + dD
kr kf

(39.9)

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. Now, at equilibrium vf = vb which implies kf [A]a [B]b = kr [C]c [D]d (39.10)

256

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.”

(39.11)

So, we have succeeded in connecting thermodynamics to kinetics BUT we have done so through the ratio of rate constants. The velocity of a reaction is lost in this ratio and hence we still can not determine the speed of a reaction from thermodynamics. Examples of rate laws Consider the (overall) reaction between molecular hydrogen and molecular iodine, H2 + I2 = 2HI. (39.12)

The observed rate laws are vf = kf [H2 ][I2 ] and vr = kr [HI]2 . This suggests that the reaction is elementary. In fact, the reaction is not elementary. Moral: Kinetics is very much an empirical science. Next consider the reaction between molecular hydrogen and molecular bromine, H2 + Br2 = 2HBr. The observed rate law for this reaction is very complicated, v= k[H2 ][Br2 ]1/2 1+
k0 [HBr] [Br2 ]

(39.13)

,

this does not obey any common form. The above two example are seemingly very similar but they have very different observed rate laws. Moral: Kinetics is very much an empirical science. Objectives of chemical kinetics

257

• 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

39.2. Determination of Rate Laws
Concentrations c(t) are measured not rates. To obtain the rate from the concentration we must take its time derivative dc(t) . That is we must measure c(t) as a dt function of time and find the rate of change of this concentration curve. The rates of chemical reactions vary enormously from sub-seconds to years. Consequently no one experimental technique can be used. • For slow reactions (hrs/days) almost any technique for measuring the concentration can be used. • 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. • Very fast (sec/subsec) reactions cause problems because the reaction goes faster than one can mix the reactants.

258

39.2.1. 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. The main problem with such a method is that randomness in the concentration measurements gets amplified when taking the derivative. 1. Method of initial velocities • for v = k[A]x [B]y rate laws. • 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. • problems 1. if the concentration drops very sharply 2. if there is an induction period 2. Method of isolation • for v = k[A]x [B]y rate laws • start with initial concentrations a and b equal to the stoichometry; this gives the overall order of x + y • flood with, say, A so v ≈ kax [B]y 39.2.2. Integrated rate laws The above differential methods look directly at the rate law which is a differential equation. The differential equation is not solved.

259

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. 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.b., vi is a negative number). b) The order need not be an integer. For example n = 3/2 is a three-halves order rate law.

− (n − 1)vi kt

260

40. Temperature and Chemical Kinetics
40.1. 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 = , d(1/T ) R where Ea is the Arrhenious activation energy. Integration of the above yields ln k = ln A −
Ea Ea =⇒ k = Ae− RT RT

(40.1) (40.2)

(40.3)

(A is the constant of integration). This is the Arrhenious equation Recall the equilibrium constant can also be obtained from kinetics
0 Kc =

kf ' Ka . kr

(40.4)

Now, take the log of this: ¸ kf = ln kf − ln kr . ln Ka = ln kr ∙ 261
261

(40.5)

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 40.1.1. Temperature corrections to the Arrhenious parameters The Arrhenious parameters A and Ea are constants. Theoretical approaches to reaction rates predict rate constants of the form k = aT j e−E /RT . Forcing this to coincide with the Arrhenious implies Ea = E 0 + jRT and A = aT j ej
0

(40.6)

(40.7)

(40.8)

(40.9)

We can verify this by starting with the Arrhenious equation and substituting the above expressions, 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)

40.2. Theory of Reaction Rates
Simple collision theory (SCT) • Bimolecular reactions (A,B) • Reaction rate determined by molecular collisions

262

— Collision frequency for A–B collisions s 8RT zAB = πσ AB L2 [A][B] πLμ where μ ≡
mA mB mA +mB

(40.11)

is the reduced mass and σAB is the collision diameter.

• The maximum reaction velocity is vmax = reaction velocity will be less because

zA B L

, 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

(40.12)

• The rate constant for a bimolecular reaction is v k= [A][B] so SCT predicts k=
pzA B e− L
Em in RT

(40.13)

[A][B]

= pπσ AB L

s

8RT − Em in e RT πLμ

(40.14)

263

• Comparison to the (temperature corrected) Arrhenious equation suggests s 8RT 1 e2 (40.15) A = pπσ AB L πLμ and 1 Ea = Emin + RT 2 (40.16)

Activated complex theory (ACT) • An intermediate active complex is formed during the reaction, e.g., A + B → (AB)‡ → products. ACT is not limited to bimolecular reactions. (40.17)

• The active complex is a state in the thermodynamic sense, thus we can apply thermodynamics to it. • For the above example, the equilibrium constant is defined as
‡ Ka =

a‡ low [‡] ' aA aB conc. [A][B]

(40.18)

264

• Definition: transmission factor, f — accounts for the fraction of activated complex that becomes product. — From statistical mechanics, it can be shown that f = kb T /h where kb is Boltzmann’s constant and h is Planck’s constant. • The reaction rate constant for reactants going to products for ACT is
‡ k = f Ka =

kb T ‡ K h a

(40.19)

• Thermodynamics tells us that
‡ 4G‡ = −RT ln Ka

(40.20)

which can be written as
‡ Ka = e−
4G‡ RT

= e−

4H ‡ RT

e

4S ‡ R

(40.21)

where 4G‡ = 4H ‡ − T 4S ‡ . • The ACT reaction rate constant now becomes k= This is Eyring’s equation kb T − 4H ‡ 4S‡ e RT e R . h

(40.22)

40.3. Multistep Reactions
Up to now, the reactions we have studied have been single step reactions. In general, there is many steps from initial reactants to final products. Reactions may occur in series or in parallel or both, in what is called a reaction network. Parallel reactions:

265

• Parallel reactions are of the form, for example,
1 A + B1 → C

k

(40.23)

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. They are of the form k1 k2 A→B→C (40.24) • The concentrations of A, 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], dt

which, 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

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

267

2. Propagation: The radical formed in the initiation step reacts with some so molecule M0 to form another molecule M00 and another radical R0 ·. This step repeats an indefinite number of times. R·+M0 → M00 + R0 ·. 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

41. Gases and the Virial Series
Unlike liquids and solids, a particular particle has much less significant interactions with the other particles. This simplifies the theoretical treatment of gases. We will now look in detail at the gases.

41.1. Equations of State
Recall from last semester several of the equations of states for gases. • The ideal gas equation of state P V = nRT. The equation of state can also be expressed in term of density ρ = ρ= mP . nRT
m V

(41.1)

(41.2)

• The van der Waals gas equation of state P = or

n2 a nRT − 2 V − nb V

(41.3)

a RT − 2, (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

• Berthelot • Dieterici

P =

nRT n2 a a RT − − = 2 2 V − nb T V Vm − b T Vm
an a

(41.5)

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)

(41.6)

• Redlich-Kwang P = (41.7)

41.2. The Virial Series
Definition: Compressibility Factor: z =
PV nRT

=

P Vm . RT

• z is unity for an ideal gas because for such a gas P V = nRT.
n • For a real gas z must approach unity upon dilution ( V → 0).

• z can be expended in a power series called the virial series. 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 +··· , + ··· . (41.8)

³n´

1 z = 1 + B(T ) Vm

1 + C(T ) Vm

1 + D(T ) Vm

(41.9)

B(T ), C(T ), etc. are called the virial coefficients. Conceptually B(T ) represents pair-wise interaction of the particles, C(T ) represents triplet interactions, etc.

270

41.2.1. 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

(41.10)

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

(41.11)

= z so z= 1 a − . b RT Vm 1 − Vm which has the power series expansion (41.13) (41.12)

The first term is of the form

1 1−x

1 = 1 + x + x2 + · · · . 1−x Therefore b a +1+ + z=− RT Vm Vm the first term is proportional to in the series expansion, hence
1 Vm

µ

b Vm

¶2

+ ··· .

(41.14)
1 Vm

and so it can be combined with the

term

µ ¶2 ³ a ´ 1 b z =1+ b− + + ··· . RT Vm Vm

(41.15)

This series can now be compared term by term to the virial series to give expression for the virial coefficients: ³ a ´ , C(t) = b2 , D(T ) = b3 , etc. (41.16) B(T ) = b − RT

271

41.2.2. The Boyle Temperature The temperature at which B(T ) = 0 is called the Boyle temperature, Tb . 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 ) + ··· . (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. 41.2.3. 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 + · · · . (41.18)

The relation of this expansion to the one in V1 can be obtained. One finds (see m homework) B(T ) B 0 (T ) = , (41.19) RT

272

C 0 (T ) = and D0 (T ) =

C(T ) − B(T )2 (RT )2

(41.20)

D(T ) − 3B(T )C(T ) − 2B(T )3 (RT )3

(41.21)

41.2.4. Estimation of Virial Coefficients The virial coefficients can be estimated using empirical equations and tabulated parameters.

• Estimates based on Beattie-Bridgeman constants: c A0 − 3, RT T A0 a B0 c − B0 b − 3 , C(T ) = RT T B0 bc D(T ) = . T3 B(T ) = B0 − where A0 , B0 , a, b, c are tabulated constants • Estimates based on critical values (we will discuss critical values shortly, for now treat them as empirical parameters): µ ¶ 9RTc 6Tc2 B(T ) = 1− 2 . (41.25) 128Pc T (41.22) (41.23) (41.24)

273

42. Behavior of Gases
42.1. P, V and T behavior
We shall briefly consider the P, V and T behavior of dense fluids (e.g., liquids). Taking volume as a function of P and T, we consider the total derivative ¶ ¶ µ µ ∂V ∂V dT + dP. (42.1) dV (T, 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 V ∂T P V ∂P T | {z } | {z }
α −κT

α is the coefficient of thermal expansion.

• At a given pressure, α describes the change in volume with temperature. • Positive α means the volume of the fluid increases with increasing temperature.

κT is the isothermal compressibility • At a given temperature, κT describes the change in volume with pressure. • Positive κT means the volume of the fluid decreases with increasing pressure. • κT is different from z, the compressibility factor. 274
274

42.1.1. α and κT for an ideal gas As an exercise we shall calculate α and κT using the ideal gas equation of state (n.b., it is, of course, absurd to treat a liquid as an ideal gas). Starting with the ideal gas law: V = nRT . P Ã ¡ ¢! µ ¶ µ ¶ nRT −1 ∂V −1 ∂ nRT −1 P − 2 κT = (42.2) = = 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

42.1.2. α and κT for liquids and solids

à ¡ ¢! ∂ nRT 1 1 P = /R = n/ ∂T VP T |{z} P
=n R / /T

(42.3)

In general, the compressibility and expansion of liquids (and solids) are very small. So one can expand the volume in a Taylor series about a known pressure, P0 . At constant T ¶ ¶2 µ ∂V ∂V (P − P0 ) + (P − P0 )2 + · · · V (P ) = V0 + ∂P ∂P T | {z T } µ
−V0 κT

(42.4)

so,

V (P ) ≈ V0 [1 − κT (P − P0 )] .

(42.5)

This approximation is quite good even over a rather large pressure range (P −P0 = 100 atm or so).

275

Likewise at constant P ¶ ¶2 µ ∂V ∂V (T − T0 ) + (T − T0 )2 + · · · V (T ) = V0 + ∂T P ∂T T | {z } µ
V0 α

(42.6)

so,

V (T ) ≈ V0 [1 + α(T − T0 )] .

(42.7)

As one final point, we can apply the cyclic rule for partial derivatives to determine the ratio κα : T ¡ ∂V ¢ ¶ µ α ∂P ∂T P cyclic = ¡ ∂V ¢ = (42.8) κT − ∂P T rule ∂T V

42.2. Heat Capacity of Gases Revisited
This section is a review from the first semester with an additional example beyond the ideal gas. 42.2.1. The Relationship Between CP and CV To find how CP and CV are related we begin with ¶ µ ∂H ,H = U + PV CP = ∂T P so µ

(42.9)

¶ ¶ ¶ µ µ ∂ (U + P V ) ∂U ∂V = +P (42.10) 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

(42.11)

P

276

thus ¶ µ ¶ ¶ µ ∂V ∂U ∂V + +P (42.12) CP = ∂V T ∂T P ∂T P V ¶ ∙µ ¶ µ ¸ ∂U ∂V = CV + +P . ∂T P ∂V T ¡ ¢ ¡ ∂U ¢ Recall the expression for internal pressure ∂V T = T ∂P V − P . 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

(42.13)

∂P ∂T

(42.14)

V

For solids and liquids: µ so ∂V ∂T ¶ = V α, µ ∂P ∂T ¶ = α κT (42.15)

P

V

α2 T V (42.16) κT For gases we need the equation of state which often is conveniently explicit in P or V but not both CP = CV + 1. Explicit in P : Replace µ 2. Explicit in V : Replace µ ∂P ∂T ¶ ∂V ∂T ¶ with − ¡ ∂T ¢V ∂P
∂V

P

¡ ∂P ¢

(42.17)

T

V

∂T with − ¡ ∂V ¢P ∂P T

¡ ∂V ¢

(42.18)

277

Examples 1. 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 (42.19) 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. One term viral equation (equation of state: V = nRT + nB). 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 (42.20) ∂T P ∂T V ∂T P ∂P T The partial derivatives are ¶ µ ∂V nR + nB 0 , = ∂T P P
∂T − ¡ ∂V ¢P = − ∂P T

µ

∂V ∂P

T

=−

nRT , P2

(42.21)

so

¡ ∂V ¢

nR P

+ nB 0 / P (R + P B 0 ) n = . nRT − P2 / RT n

(42.22)

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

(42.23)

or

(42.24)

278

42.3. Expansion of Gases
Expanding gases do work: −w = Z
V2

Pex dV

(42.25)

V1

As we learned last semester the value of w depends on Pex during the expansion. Recall that if the expansion is reversible, there is always an intermediate equilibrium throughout the expansion. Namely Pgas = Pex . So, −wrev = For an ideal gas (P =
nRT ) V

Z

V2

Pgas dV

(42.26)

V1

this becomes Z
V2

−wrev =

V1

µ ¶ V2 nRT dV = nRT ln V V1

(42.27)

Also recall that −wrev is the maximum possible work that can be done in an expansion. −wrev = −wmax . 42.3.1. Isothermal and Adiabatic expansions We shall consider two limits for the expansion of gases 1. Isothermal expansion T is constant 2. Adiabatic expansion q = 0.

Isothermal expansion • For the case of a ideal gas, U (T, V ) = U(T ) (independent of V ). So for isothermal expansion 4U = 0 = q + w =⇒ q = −w.

279

Adiabatic expansion • Since q = 0, dU = dw = −Pex dV = −P dV (reversible). • For an ideal gas dU = −P dV = −nRT dV V (42.28)

42.3.2. Heat capacity CV for adiabatic expansions Considering an ideal gas going adiabatically from (T1 , V1 ) to (T2 , V2 ). Recall ¶ µ ∂U CV = =⇒ dU = CV dT ∂T V So from above CV dT −nRdV −nRT dV =⇒ = V T V Going from (T1 , V1 ) to (T2 , V2 ): CV dT = Z
T2

(42.29)

(42.30)

T1

CV dT = T

Z

V2

V1

−nR dV. V

(42.31)

If CV (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ V2 T2 ¯ = −nR ln (42.32) CV ln T1 V1 ¯ where CV = 1 (CV (T1 ) + CV (T2 )) . Or, in terms of molar heat capacity
2

T2 ¯ CV m ln T1

µ

V2 = −R ln V1

µ

(42.33)

280

42.3.3. 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, dH = dU + P dV + V dP (because both P and V can, in general, change)

/ / dH = dq + dw + P dV + V dP
dH = V dP. Now, CP = µ ∂H ∂T ¶

(42.34)

=⇒ dH = Cp dT = V dP

(42.35)

P

For an ideal gas this becomes

Cp dT = Going from (T1 , P1 ) to (T2 , P2 ): Z T2
T1

nRT dP P Z

(42.36)

CP dT = T

P2

P1

nR dP. P

(42.37)

If CP (T ) is reasonably constant over the internal T1 to T2 then this is approximately µ ¶ µ ¶ P2 T2 ¯ = nR ln (42.38) CP ln T1 P1 ¯ where CP = 1 (CP (T1 ) + CP (T2 )) . Or, in terms of molar heat capacity
2

T2 ¯ CP m ln T1

µ

P2 = R ln P1

µ

(42.39)

From the above two cases µ ¶ µ ¶ µ ¶ R −R P2 V2 T2 = ¯ ln = ¯ ln ln T1 P1 V1 CP m CV m

(42.40)

281

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

(42.41)

V1 = γ ln V2

µ

V1 = ln V2

µ

¶γ

(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 ,

(42.43)

42.3.4. Joule expansion Consider a gas expanding adiabatically against a vacuum (Pex = 0). In this case q = 0 (adiabatic) and w = 0 (since −dw = Pex dV ).

282

This implies 4U = q + w = 0. Internal energy is constant. We want to find Identity: ¡ ∂T ¢
∂V

(42.44)

U

. ¶ µ ¶ ¶ µ µ ∂U ∂U ∂T 1 =− = ∂U V ∂V T CV ∂V T | {z }
1/CV

µ

∂T ∂V

(42.45)

U

For an ideal gas ∂V T = 0 (since U(T, V ) = U(T )). Thus in as much as the ¡ ∂T ¢ gas can be considered ideal ∂V U = 0. That is, for Joule type expansion the temperature of the gas does not change. For real gases this is not strictly equal to zero. 42.3.5. Joule-Thomson expansion Consider the adiabatic expansion as illustrated by the figure below

¡ ∂U ¢

283

The work done on the left is wL = −P1 4V = −P1 (0 − V1 ) = P1 V1 . The work done on the right is wR = −P2 4V = −P2 (V2 − 0) = −P2 V2 . Now, 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. We want to find Identity: µ ¡ ∂T ¢
∂V

(42.46)

(42.47)

(42.48)

(42.49)

H

≡ μ. (the Joule-Thomson coefficient). ¶ µ ¶ ¶ µ µ ∂H ∂T 1 ∂H =− = =μ ∂H P ∂P T CP ∂P T | {z }
1/CP

∂T ∂P

(42.50)

H

284

Recall the useful identity µ Thus ∂H ∂P ¶ =V −T µ ∂V ∂T ¶ (42.51)

T

P

¡ ¢ −V + T ∂V P ∂T μ= CP

(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 . μ = CP m Limts: • Low T : B 0 is positive and B is negative, so μ is positive–the gas cools upon expansion • High T : B 0 is nearly zero and B is positive, so μ is negative–the gas warms upon expansion • The Joule-Thomson inversion temperature is the temperature where μ = 0. (42.53)

285

43. Entropy of Gases
43.1. Calculation of Entropy
Entropy must be calculated along reversible paths. This is not a problem though since entropy is a state function. Entropy change for changes in temperature. • At constant V : — dU = dq + dw
dq=CV dT

=⇒

dU = CV dT, but also dU = T dS. So Z T2 CV CV dT =⇒ 4S = dT. dS = T T T1

(43.1)

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 . So dH = dq =⇒ dq=T dS dH = CP dT, but also dH = T dS. So Z T2 CP CP dT =⇒ 4S = dT. (43.2) 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 . 286
286

• Using the equation of state nRdV =⇒ 4S = dS = V

Z

V2

V1

V2 nR dV = nR ln . V V1

(43.3)

• Using the equation of state to express V1 and V2 in terms of P1 and P2 . V2 P2 dS = nR ln = nR ln P2 = −nR ln . V1 P1 /R / n / T
P1

/R / n / T

(43.4)

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. Entropy of Mixing of an ideal gas

• Since the gas is ideal, there are simply two separate equations: 4SA = nA R ln and 4Smix = 4SA + 4SB (43.6) VA + VB , VA 4SB = nB R ln VB + VA VB (43.5)

287

• Recall Avogadro’s principle: n ∝ V for an ideal gas. So. ⎛ ⎞
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 } (43.7)

43.1.1. Entropy of Real Gases Consider the question: How does S → S ideal as P → 0 ? Use Maxwell relation nRT + nB. P So ¡ ∂S ¢ µ ∂S ∂P
∂P T

= −

¡ ∂V ¢
∂T

P

and single term viral equation, V =

Hence

T

∂V =− ∂T

µ

P

=−

nR − nB 0 P

(43.8)

µ ¶ → nR P2 → 0 − nB dP =⇒ S2 − S1 = −nR ln dS = − − nB 0 (P2 − P1 ) P P1 P2 P1

(43.9)

For an ideal gas B 0 = 0, so
ideal ideal S2 − S1 = −nR ln

(43.10)

Thus
ideal ideal S2 − S1 = S2 − S1 − nB 0 (P2 − P1 )

(43.11)

Letting P1 → 0 and P2 → P θ (Standard pressure 1 bar), this becomes S2 − / 1 S
ideal ideal = S2 − / 1 S ideal

− nB 0 (P2 − P1 )

(43.12)

ideal Defining S2 , P2 → P θ as S θ . So,

S(P θ ) = S θ − nB 0 P θ

(43.13)

288

The entropy at any P and T can be obtained expresses as S(T, P ) = S ideal (T, P ) − nB 0 P Thus S(T, P ) = S θ (T ) − nR ln P − nB 0 P Pθ (43.14)

(43.15)

289

Key Equations for Exam 3
Listed here are some of the key equations for Exam 3. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

Equations
• The Maxwell’s distribution of speeds is F (v) = 4π µ m 2πkb T

¶3 2

e 2kb T v2 .

−mv2

(43.16)

• The average speed of a particle is hvi = • The mean free path is

r

8RT πM

(43.17)

RT λ= √ 2P Lπσ 2

(43.18)

290
290

• The reaction velocity is v=

1 d[I] vi dt

(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

(43.21)

• 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) (43.22)

• The van der Waals gas equation of state: P = • Compressibility Factor: a RT − 2. Vm − b Vm P Vm PV = . nRT RT (43.24)

z=

(43.25)

• 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

(43.26)

(43.27)

291

Part VIII More Thermodyanmics

292
292

44. Critical Phenomena
44.1. Critical Behavior of fluids
The point on the top of the coexistence curve is called the critical point. It is characterized by a critical temperature, Tc , and a critical density ρc .

Law of rectilinear diameters: The average density [ρave = 1 (ρliq + ρvap )] is 2 linear in temperature.

293
293

44.1.1. 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. Simple gas laws do not work well near critical points.

294

44.1.2. Gas Constants from Critical Data Consider the van der Waals equation at the critical point (Pc , Tc , Vmc ) Pc = a RTc − 2 . Vmc − b Vmc
2

(44.1)

dP d There is an inflection point ( dVm = 0, dVP = 0) at the critical point. So, 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 , Tc and Vmc gives Vmc = 3b, 8a , Tc = 27bR a . Pc = 27b2

¯ d2 P ¯ ¯ = 2RTc − 6a = 0 2¯ 4 dVm c (Vmc − b)3 Vmc

(44.3)

(44.4) (44.5) (44.6)

These values can be used to find the compressibility factor, z, at the critical point zc = Pc Vmc 3 = = 0.375. RTc 8 (44.7)

Notice that both a and b whose values depend on the particular gas have dropped out. That is (for the van der Waals Equation) zc = 0.375 for all gases. The other equations of state give similar results van der Waals Berthelot Dieterici Redlich-Kwong zc 3/8 = 0.375 3/8 = 0.375 2/e2 ' 0.27 0.33

295

44.2. The Law of Corresponding States
We have found that zc is predicted by the equations of state to be independent of the particular gas. This is actually not too far from the truth experimentally. One can define unitless “reduced” variables Tr = T /Tc , Pr = P/Pc , and Vr = V /Vc . Then zr = Pr Vrr . RT zr is a “universal” function–it is nearly the same for all gasses. ∗ ∗ See Fig. 1.18 Laidler&Meiser ∗ ∗

44.3. Phase Equilibrium
Consider a homogeneous substance consisting of two phases α and β at a constant T and V. Suppose some amount of material, dn, goes from α → β • (dAα )T = −P dVα − μα dn • (dAβ )T = −P dVβ + μβ dn
= 0 since V is constant

• (dA)T,V = −P

For a spontaneous process A deceases (dA < 0)

z }| { (dVα + dVβ )

¡ ¢ + μβ − μα dn

At equilibrium dA = 0. This implies μβ = μα is the condition for equilibrium. When α, β denote liquid (or solid) and vapor phases, then for a given T , the pressure of the system when μβ = μα is the called the vapor pressure of the material at temperature T.

296

¡ ¢ For phase changes at constant T and P then (dG)T,P = μβ − μα dn. So again μβ = μα is the condition for equilibrium. 44.3.1. The chemical potential and T and P How does μ vary with T and P ? Generally for homogeneous substances, dG = −SdT + V dP + μdn Now, ∂G S=− ∂T So, µ ∂S ∂n ¶ µ ¶ (44.8)

(44.9)

P,n

P,T

µ ¶ ∂ ∂G ∂μ ∂ ∂G =− =− =− . ∂n ∂T ∂T ∂n ∂T P µ ∂μ ∂T ¶ = −Sm . = Vm .

(44.10)

But S = nSm (T, P ) so,

(44.11)

P

Similarly,

µ

∂μ ∂P

(44.12)

T

Now the total differential of μ is
m z z m µ }|¶ { µ }| ¶ { ∂μ ∂μ dT + dP dμ(T, P ) = ∂T P ∂P T dμ(T, P ) = −Sm dT + Vm dP

−S

V

(44.13)

297

44.3.2. The Clapeyron Equation At equilibrium μβ = μα so, −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

(44.14)

=

This is the Clapeyron Equation

4φ Hm T 4φ Vm

(44.15)

(44.16)

44.3.3. Vapor Equilibrium and the Clausius-Clapeyron Equation The above Clapeyron equation applies to any phase transition; consider the liquidvapor phase transition. Now 4v V = Vm,vap − Vm,liq ' Vm,vap Assuming the vapor phase obeys the ideal gas equation of state, 4v V = RT P (44.18) (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

(44.19)

Collecting the T ’s on one side of the equation and the P ’s on the other we get (44.20)

= d(ln P ) and

dT T2

= −d(1/T ) so this becomes 4v Hm d(1/T ) R (44.21)

d(ln P ) = −

298

Rearranging again leads to 4v Hm d(ln P ) =− d(1/T ) R This is the Clausius-Clapeyron equation. (44.22)

44.4. Equilibria of condensed phases
Examples • Solid—liquid — ice—water, 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. “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 (44.23)

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 ) (44.24) α β

299

Thus for any given T only one P allows for equilibrium. Recall the Clapeyron equation 4f Hm Hmβ − Hmα dP = = dT T 4f Vm T (Vmβ − Vmα ) (44.25)

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 = (44.26) 4f Hm 4f Hm Tf → T
ª where Tf is the freezing temperature at standard pressure (1 bar).

44.5. Triple Point and Phase Diagrams
Definitions • Phase Diagram: A graph of P vs. T for a system which shows the lines of equal chemical potential • Critical Point: The terminal point of the liquid-vapor line. At temperatures above the critical point there is no distinction between vapor and liquid. • Triple Point: The point where all three phases coexist in equilibrium: μsolid = μliq = μvap (44.27)

300

45. Transport Properties of Fluids
Transport properties of matter deal with the flow (or flux) of some property along a gradient of some other property. Flux: movement of something through a unit area. We now consider three transport properties of fluids: 1. Diffusion: The flux of material down a concentration gradient 2. Viscosity: The flux of momentum down a velocity gradient 3. Thermal Conductivity: The flux of energy down a temperature gradient

∗ ∗ See Transport Phenomena handout ∗ ∗

45.1. Diffusion
At equilibrium concentration on a bulk solution will be uniform. So if there exists a concentration gradient there will be a net flux, J, of material from high concentration to low concentration so as to establish an equilibrium. J= 1 dn A dt (45.1)

301
301

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). 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 . ∂t ∂x ∂x If D is truly constant we get Fick’s second law of diffusion: ∂ 2C ∂C =D 2. ∂t ∂x (45.4) (45.3) (45.2)

(45.5)

302

The solution of this partial differential equation depends on the boundary conditions. Numerous methods of solution exist for this equation but they are beyond the scope of the course. The solution for two special boundary conditions are of interest and will simply be presented here without derivation 1. Point source solution
x2 C0 C(x, t) = √ e− 4Dt 2 πDt

(45.6)

2. Step function solution # Z √x 4Dt 1 1 2 −√ e−y dy C(x, t) = C0 2 π 0 ¶¸ ∙ µ x 1 C0 1 − erf √ = 2 4Dt ¶ µ 1 x = C0 erfc √ 2 4Dt " (45.7)

where erf and erfc are tabulated functions respectively called the error function and complementary error function.

45.2. Viscosity
Viscosity, η, is the resistance to differential fluid flow, i.e., The tendency of a liquid to flow at the same velocity throughout.

303

dv The frictional (viscous) force is F = ηA dx . (The units of η are g = cm·s .)

mass . lenght·time

1 poise

Poiseuille’s Formula • Applies to Laminar (nonturbulent) flow • For a liquid flowing trough a tube (radius r, length l), the volume of flow 4V in time 4t is πr4 4P 4V =− (45.8) 4t 8ηl where 4P is the driving pressure, i.e., the difference in pressure on either side of the tube. • For a gas 4V πr2 = 4t 16ηl µ
2 Pi2 − Pf P0

where Pi is the inlet pressure, Pf is the outlet pressure and P0 is the pressure at which the volume is read.

(45.9)

Stoke’s law: spheres falling through fluids

304

• The frictional force (exerted upwards) is proportional to velocity: Ff = −fv. Stokes showed f = 6πηr • Gravitational force (exerted downwards): Fg = gravitational acceleration (9.8 m/s2 ).
4πr3 (ρ − ρ0 )g, 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)

(45.11)

• Related to diffusion constant:

=

kT 6πηr

(45.12)

45.3. Thermal conductivity
(This section closely follows parts of chapter 8 in Transport Phenomena by R.B. Bird, W.E. Stewart and E. N. Lightfoot Wiley New York 1960) The thermal conductivity, κ, of a material is a measure of the tendency of energy in the form of heat to flow through the material. Consider a slab of solid material of area A between two large parallel plates a distance D apart. 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

Under such conditions, a linear steady state temperature distribution across the material is established. And a constant rate of heat flow dq is needed to maintain dt the temperature difference 4T = (T1 − T2 ) 4T 1 dq = −κ . (45.13) 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 , (45.14) A dt dx where Qf is the heat flux. This is called Fourier’s law of heat conduction (one-dimensional version). Thermal conductivities are positive quantities so Fourier’s law says that heat flow down a temperature gradient, i.e., from hot to cold. 45.3.1. 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, whereas the thermal conductivity of most liquids decrease with increasing temperature.

306

45.3.2. Thermal Conductivity of Solids For the most part, 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. Dry porous materials are poor heat conductors Rule of Thumb: Thermal conductivity and electrical conductivity go hand in hand. The Wiedemann, Frantz and Lorenz equation relates the thermal conductivity to electrical conductivity, κel for pure metals: κ = L = const. κel T where L is the Lorenz number (typically 22 to 29 × 10−9 V2 /K2 ). 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. The Wiedemann, Frantz and Lorenz equation breaks down at low temperature because metals become superconductive. There is no analog to superconductivity for thermal conductivity. (45.15)

307

46. Solutions
Solutions are mixtures of two or more pure substances. So, in addition to the parameters needed to characterize a pure substance, one also needs to keep track of the amount of individual species in solution

46.1. Measures of Composition
There are several measures of composition of solutions • mole ratio r =
n1 n2 n2 , n1 +n2

• mole fraction X2 = • molality m = • Molarity c2 =

X1 = 1 − X2

1000X2 , M1 X1

where M1 is the molecular weight of species 1

n2 L solution

46.2. Partial Molar Quantities
Thermodynamic properties, in general change upon mixing X 4mix = properties of soln − properties of pure. For example, 4mix V = Vsoln − Vsolute − Vsolvent Consider a thermodynamic quantity, say, volume. 308
308

(46.1)

(46.2)

In general, it is a function of T, P, n1 and n2 : V (T, P, n1 , n2 ). So, the total derivative is ¶ ¶ µ ¶ ¶ µ µ µ ∂V ∂V ∂V ∂V dV = dT + dP + dn1 + dn2 , ∂T P,n1 ,n2 ∂P T,n1 ,n2 ∂n1 T,P,n2 ∂n2 T,P,n1 (46.3) ³ ´ ∂V ¯ ≡ Vi , the partial molar volume. ∂ni
T,P,nj

Similarly ¶ ¶ ¶ ¶ µ µ µ µ ∂G ∂G ∂G ∂G dT + dP + dn1 + dn2 , dG = ∂T P,n1 ,n2 ∂P T,n1 ,n2 ∂n1 T,P,n2 ∂n2 T,P,n1 (46.4) ³ ´ ∂G ≡ μi . ∂ni
T,P,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, rather than simply the molar free energy as it was earlier. 46.2.1. Notation The study of solutions brings with it here for future reference. 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

46.2.2. Partial Molar Volumes Consider the partial molar volume For constant T and P ¯ ¯ dV = V1 dn1 + V2 dn2 (46.5) ¯ Now, Vi depends on concentration, so change each amount of substance proportional to the amount substance present, dn1 = n1 dλ, So, dn2 = n2 dλ. (46.6)

That is, the total volume of the solution is equal to the sum of the partial molar volumes each weighted by their respective number of moles. The total volume, however, is not necessarily the mole weighted sum of the volumes of each component in its pure (unmixed) state. 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

(46.7)

(46.8)

4mix V can be positive, negative or zero. For example,

1. one unit of baseballs are mixed with one unit of basketballs. 4mix V < 0. 2. one unit of baseballs are mixed with one unit of books. 4mix V > 0.

310

46.3. Reference states for liquids
For liquids there are two more convenient ideal states 1. neat (pure) solvent limit 1. all neighboring molecules are same as the given molecule 2. the ideal state for Raoult’s law 2. infinite dilution limit 1. all neighboring molecules are different than the given molecule 2. the ideal state for Henry’s law

Raoult’s law limit 46.3.1. 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

Also recall that the mathematical definition of activity ai of some species i is implicitly stated as ai lim =1 (46.9) ζ→ζ ª g(ζ) where g(ζ) is any reference function (e.g., pressure, mole fraction, concentration etc.), and ζ ª is the value of ζ at the reference state. This implicit definition is awkward so for convenience one defines the activity coefficient as the argument of the above limit, γi ≡ which we can rearrange as ai = γ i g(ζ). (46.11) 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. 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). μi − μª = RT ln ai . (46.12) i ai g(ζ) (46.10)

46.3.2. Raoult’s Law In discussing both Raoult’s law and Henry’s law, we are describing the behavior of a liquid solution by measuring the vapor (partial) pressures of the components

312

For simplicity we consider here only a two component solution. dG = μ1 dn1 + μ2 dn2 . Take differential change along a line of constant concentration, so dG = (μ1 n1 + μ2 n2 ) dλ then G = μ1 n1 + μ2 n2 . Recall that 4mix G = G(soln) − G(pure components) Hence, 4mix G = μ1 n1 + μ2 n2 − μ• n1 − μ• n2 1 2 (46.17) (46.16) (46.15) (46.14) (46.13)

= (μ1 − μ• ) n1 + (μ2 − μ• ) n2 . 1 2 ai low P Pi ' RT ln • , • ai Pi (46.18)

Now, μ1 − μ• = RT ln 1

where Pi is the vapor pressure of the ith component above the solution.

313

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

(46.19)

(46.20)

46.3.3. Ideal Solutions (RL) Raoult’s Law: Pi = Xi Pi• (46.21)

That is, 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. The change in free energy upon mixing for solutions ideally obeying Raoult’s law is à ! • • X1 P/ X2 P/ id(RL) 1 2 4mix G = RT n1 ln + n2 ln (46.22) • • P1 / P2 / 4mix G = RT (n1 ln X1 + n2 ln X2 ) Again, this is for an ideal solution in the Raoult’s Law sense. From ¶ ¶ µ ∂G ∂ (G/T ) S=− and H = − , ∂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)

(46.23)

(46.24)

(46.25)

(46.26)

314

(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. The reference function is g(ζ) = ζ = Xi . and the reference state is Xi = 1 So, ai =1 Xi →1 Xi lim implies ai and γ i
(RL) (RL) (RL)

(46.27)

= γi

(RL)

Xi ,

(46.28)

→ 1 as Xi → 1

Deviations from Raoult’s Law Raoult’s law is a purely statistical law. It does not require any kind of interaction among the constituent particle making up the solution. Since, in reality, there are specific interactions between particles, real solutions generally deviate from Raoult’s law. 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. • negative deviation: the molecules prefer to be around other types of molecules than themselves. • no deviation: the molecules have no preference.

315

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 example, for a given component, mixing with one substance may lead to a positive deviation but mixing with another substance may lead to a negative deviation.

Positive deviation from Raoult’s lawNegative deviation from Raoult’s law 46.3.4. Henry’s Law Henry’s Law: Pi = kXi Xi , where kXi is the Henry’s law constant, kXi = lim µ Pi Xi ¶ (46.30) (46.29)

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), i.e., at infinite dilution.

316

The Reference State (HL) Referring to the definition of activity again we see that the reference function is g(ζ) = ζ = Xi . and the reference state is now Xi = 0 So, (HL) ai lim =1 (46.31) Xi →0 Xi implies (HL) (HL) = γ i Xi , (46.32) ai → 1 as Xi → 0 and γ i If instead of mole fraction, molality or molarity is used then ai and ai respectively. 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. But, they apply to opposite species in the solution. Raoult’s law applies to the dominant species, X1 → 1, whereas Henry’s law applies to the subdominant species X2 → 0. So, 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

(46.33)

= γ Mi Mi

(HL)

(46.34)

317

46.4. 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 46.4.1. Freezing Point Depression At Tf (freezing point), μ1 (solid) = μ1 (soln). | {z }
μs 1

318

Using the Raoult’s law reference state (since we are interested in the behavior of the dominant species), 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
∂μ ∂T

(46.35)

(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

(46.37)

• For small changes in the freezing point we may approximate T by Tf in the integrand. So, Z Tf −4f H 4f H ln a1 ' dT = Θ, (46.38) •2 •2 • RTf Tf RTf • where Θ ≡ Tf − Tf . The freezing point depression is

Θ=− 46.4.2. Osmotic Pressure

RTf•2 ln a1 4f H

We consider the osmotic pressure at a constant temperature, T. (so, dG = V dP ).

319

In the above figure μ1 (left) = μ1 (right), hence ¯ μ• = μ• + RT ln a1 + V1 Π, 1 1 (46.39)

¯ where V1 is the partial molar volume of the solvent in solution (difficult to measure) and Π is the hydrostatic (osmotic) pressure. From the above equation

¯ V1 Π RT • ¯ Now we make the approximations V1 = Vm1 , a1 = X1 = 1 − X2 : ln a1 = ln(1 − X2 ) =
• Vm1 Π RT

(46.40)

(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 , 2 3

(46.42)

'

n2 n1

for dilute solutions. Thus
1 z }| { • • V Π n1 Vm1 Π n2 , ' m1 =⇒ n2 ' n1 RT RT

V•

(46.43)

320

or, Π=

where c is the concentration of the solute.

n2 RT = cRT, V1• |{z}
'c

(46.44)

Note the similarity of this equation with the ideal gas equation: P = cRT. Thus the solute in a very dilute solution behaves as if it were an ideal gas.

321

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. 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. This allows us to make a stronger connection between thermodynamics and kinetics. The main concept of this approach is the idea of entropy production and, ultimately, entropy production per unit time–how fast we are producing entropy.

47.1. Fundamentals
We know the difference between reversible and irreversible processes from before. However, we will state their respective definitions here in a manner best suited for this chapter.

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322

Reversible process: dynamical equations are invariant under time inversion (t → −t). • e.g., the one dimensional wave equation, 1 ∂ 2 u ∂ 2 u t→−t 1 ∂ 2 u ∂2u 1 ∂2u ∂2u = 2 =⇒ = 2 =⇒ = 2, 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). • e.g., the one dimensional heat equation, ∂ 2 T t→−t 1 ∂T ∂ 2T ∂2T 1 ∂T 1 ∂T = = = =⇒ =⇒ − , κ ∂t ∂x2 κ ∂(−t) ∂x2 κ ∂t ∂x2 is not invariant under time reversal. (47.2) (47.1)

We will be concerned with the change in entropy, dS, which can be split into two components dS = de S + di S. Definitions • de S is the change in entropy due to interactions with the exterior environment. • di S is the change in entropy due to internal changes of the system The quantity di S is called the entropy production.

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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. 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, di S = dS ≥ 0, holds.

47.2. The Second Law
As you might expect, the second law underlies all the concepts of this chapter. We need a “local” formulation of the second law: • Absorption of entropy in one part of the system, compensated by a sufficient production in another part is prohibited — i.e., in every macroscopic region of the system the entropy production due to irreversible processes is positive. This is simply another in our long list of alternative statements of the second law.

324

I II

Considering the above figure of an isolated system, we write the principle of Clausius as dS = dS I + dS II ≥ 0. (47.3) The local formulation statement implies di S I ≥ 0 and di S II ≥ 0 (47.4)

¡ ¢ and the possibility of, for example, di S I < 0 and di S II > 0 such that di S I + S II > 0 is excluded.

47.3. Examples
The idea of entropy production can be applied to any of the processes we have talked about; mixing, phase changes, heat flow, chemical reactions, etc. As example we now consider the last two of these: heat flow and chemical reactions.

325

47.3.1. 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

(47.5) we get (47.6)

We are now interested in exposing the time dependence, so, using Qf = κA4T q =− 4t D in differential form this is

dT dq = −κA . (47.7) dt dx Example: Find the entropy production in a system consisting of two identical connected blocks of metal (I and II), 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.

326

Considering the whole system dqI dqII + T1 T2
e i z }| { z }| { de qI de qII di qI di qII = + + + . T1 T2 T1 T2

d S

dS

dS =

(47.8)

The quantity de qj is the amount of heat supplied by the environment to hold block j at its fixed temperature. 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 . Using this we see that the entropy production is µ ¶ 1 1 , − di S = di qI T1 T2 which we see is positive because di qI < 0 when T1 > T2 . We have still not made a connection to kinetics. To do so we must consider the entropy production per unit time
di S . dt

(47.9)

(47.10)

327

For this example di qI di S = dt dt From chapter 24 we know

µ

1 1 − T1 T2

¶ (47.11) ¶

−Aκ4T di qI = . dt D So, −Aκ4T di S = dt D µ 1 1 − T1 T2

(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 = . (47.13) dt dt ¯ Using the above expression for heat flow gives us T since, − ¢ ¢ κ/ κ/ /A ¡ / A ¡¯ ¯ ¯ T1 + T2 ; T1 − T = − T − T2 ⇒ T = 2 D / D / (47.14)

a result we might have guessed.

47.3.2. Entropy Production due to Chemical Reactions Definitions: 1. Chemical affinity: a ≡ − (4rxn G)T,P = − P − i vi μi P
i

vi μi and a ≡ − (4rxn A)T,V =

2. Extent of reaction: ξ is defined by dξ = dni , where ni is the number of moles vi of the ith component and vi the stoichiometric factor of the ith component.

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• e.g., 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,V = X
i dξ dt

dnH2 dnNH3 dnN2 = = (−1) (−3) (2)

(47.15)

(47.16)

but (dA)T,V so

µ ¶ 1 dni = −adξ μi dni = vi μi vi | i {z }| {z } X
−a dξ −adξ

(47.17)

z }| { z }| { (dA)T,V dq − = (dU)T,V − T dS ⇒ dS = T T
dq
e i z}|{ z}|{ dq adξ + dS = T T

(47.18)

d S

dS

(47.19)

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 (47.20)

We see that for a spontaneous process the entropy production per unit time is positive. This is because a = − (4rxn A)T,V is positive as is v.

329

Simultaneous Reactions For N simultaneous chemical reactions, the entropy production per unit time generalizes to N 1X di S = aj vj ≥ 0. (47.21) dt T j=1

The second law requires that the total entropy production for simultaneous reactions is positive. 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.

For example in a system of two coupled reactions we could have a1 v1 < 0, a2 v2 > 0 such that a1 v1 + a2 v2 > 0.

47.4. 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. We just saw an example of such a situation with the discussion of simultaneous reactions. Thermodynamic coupling need not be confined to coupling between the same types of processes. That is, diffusion is the flux of matter down a concentration gradient. The socalled Soret effect is flux of matter down a temperature gradient. Conversely, the so-called Dufour effect is heat flux down a concentration gradient

330

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

47.5. 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. The ensemble evolves in two ways • Reversibly — A second perturbation can “undo” or reverse the evolution. • 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.

331

• A strong signal is seen because all the spinning nuclei cooperate. • Each nucleus is in a slightly different environment so each spin frequency is slightly different. • 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. • 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.

332

Key Equations for Exam 4
Listed here are some of the key equations for Exam 4. This section should not substitute for your studying of the rest of this material. 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. The equations are collected here simply for handy reference for you while working the problem sets.

Equations
• The Clapeyron Equation is 4φ Hm dP = . 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 (47.24) (47.23) (47.22)

333
333

• Fick’s second law of diffusion:

∂ 2C ∂C =D 2. ∂t ∂x

(47.25)

• Relation between the viscosity and the diffusion constant: D= kT f
f =6πηr

=

kT . 6πηr

(47.26)

• Fourier’s law of heat conduction is

dT 1 dq = Qf = −κ . A dt dx X

(47.27)

• Mixing 4mix = properties of soln − • Chemical potential • Raoult’s Law: • Raoult’s law reference ai • Henry’s Law:
(RL)

properties of pure.

(47.28)

μ = μª + RT ln a

(47.29)

Pi = Xi Pi•

(47.30)

= γi

(RL)

Xi ,

γi

(RL)

→ 1 as Xi → 1

(47.31)

Pi = kXi Xi . µ ¶

(47.32)

where kXi is the Henry’s law constant, kXi = lim • Henry’s law reference ai
(HL) Xi →0

Pi Xi

.

(47.33)

= γi

(HL)

Xi ,

γi

(HL)

→ 1 as Xi → 0.

(47.34)

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Index
absorption spectroscopy 241 activity 146, 311 mathematical definition of 146 activity coefficient 146, 312 adiabatic expansion 280 and heat capacity 280 adiabatic wall 120 angular momentum addition of 202 classical 192 eigenfunctions for 199, 219 jj coupling 202 LS coupling 202 quantum numbers 199, 219 spin 201 angular momentum quantum number 52 antibonding orbital 71 Arrhenious activation energy 261 Arrhenious equation 261, 291 temperature corrected 262 atomic orbitals 49 chemists picture 50 physicists picture 50 aufbau principle 58 average value theorem 29 Berthelot gas 13, 270 binominal coefficient 90 blue sky 81 Bohr model 18 335
335

Bohr radius 19 Boltzmann distribution 10, 96, 131 Boltzmann’s equation 90, 97, 124, 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, 178 partition coefficient 174 Born—Oppenheimer approximation 62, 99, 235, 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

Clapeyron equation 298, 300, 333 Clausius-Clapeyron equation 299, 333 coefficient of thermal expansion 274 coexistence curve 293 colligative properties 318 commutator 30, 189 completeness 191 complimentary variables 30 compressibility factor at the critical point 295 compressibilty factor 270, 291 configuration 90 confluent hypergeometric functions 65 correspondence principle 41 critical point 300 cyclic rule 14, 108 cylindrical symmetry 69 Debye—Huckel limiting law 164, 178 Debye—Huckel theory 163 Debye—Huckel—Guggenheim equation 164 Debye’s law 129, 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, 231 electrolytes strong 161 electrophoretic effect 167 elementary reactions 255 and stoichiometry 256 molecularity 256 emission spectroscopy 241 enemble 89 ensemble average 103, 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, 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

equlibrium constant 153 Euler’s identity 4 expansion of gases 111 reversible 114 extent of reaction 328 Eyring’s equation 265, 291 fermions 56 Fick’s first law 302, 333 Fick’s second law 302, 334 first law of thermodynamics 121, 133 flipping coins 90 fluctuation 92 fluorescence 242 stokes shift 242 Fourier’s law of heat conduction 306, 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, 44, 86 potential energy 39 Schrodinger equation for 39 heat 109 sign convention 110 heat capacity 115, 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, 316, 334 Henry’s law constant 316, 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, 86 Hamiltonian 47 normalization constant 49, 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, 121 intramolecular vibrational relaxation (IVR) 242

337

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, 290 mean free path 253, 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, 86 Schrodinger equation for 65 wavefunction for 65 Morse potential 64, 86, 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

particle in a box 31, 181 energy levels 183 energy levels for 34, 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, 44, 218 particle on a ring 194 boundary conditions 194 energy levels for 195, 218 Hamitonian for 194 wavefunctions for 195, 218 partition coefficient 154 and drug delivery 155 for the Born model 174 partition function canonical 96, 131 electronic 101 grand canonical 97 isothermal—isobaric 97 microcanonical 96 molecular 100 rotational 101, 132 translational 101, 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, 133 Raman scattering 80 Raman spectroscopy 66, 233 and the character table 234 Raoult’s law 311, 312, 314, 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, 82, 87 reaction velocity 255, 291 reciprocal rule 108 red sunsets 82 Redlich-Kwang gas 270 reference states 147 relationship between CP and CV 139, 276 relaxation effects 167 rigid rotor 200 degeneracy of 235, 248 energy 235, 247 rotational energy levels 200, 219

339

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, 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, 200 spin 201 quantum number 51, 53 wavefunction 51 spin orientation quantum number 51, 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, 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, 133 tips for solving problems 2 total derivative 107 transfer matrix 11 triple point 300 two level system 211 ‘left’ and ‘right’ states 213, 219 Hamiltonian for 212 Tyndall scattering 84 ungerade 69 van der Waals equation

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